Curable composition, method for producing pixel, film, solid-state imaging element, image display device, and photopolymerization initiator

Abstract

A curable composition according to the present invention contains a photopolymerization initiator, a polymerizable compound, and a solvent. The photopolymerization initiator contains a compound A represented by formula (1A) or formula (1B). Also provided are a method for manufacturing a pixel in which the aforementioned curable composition is used, a film, a solid-state imaging element, and an image display device. The photopolymerization initiator contains a compound represented by formula (1A) or formula (1B).

Description

Curable composition, pixel manufacturing method, film, solid-state imaging device, image display device, and photopolymerization initiator

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

[0002] Curable 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 are formed by forming a pattern by a photolithography method using a curable composition containing a photopolymerization initiator including an oxime compound with a specific structure and a polymerizable compound.

[0004] International Publication No. 2015 / 152153

[0005] When forming pixels by forming a pattern using a curable composition by a method such as photolithography, the formation is generally achieved through the steps of forming a curable composition layer on a support using the curable composition, exposing the curable composition layer to light in a pattern, and developing and removing the unexposed portions of the curable composition layer. Furthermore, if exposure treatment is performed without sufficient removal of the solvent from the curable composition layer, the resolution of the pattern is likely to decrease. Therefore, generally, before exposing the curable composition layer, the solvent contained in the curable composition layer is removed by drying (pre-baking).

[0006] However, many of the photopolymerization initiators that have been used conventionally have low thermal stability, and the heating temperature during drying is limited to about 100°C. If the curable composition layer is dried at a temperature higher than this, the photopolymerization initiator may decompose during drying, resulting in a risk of reduced sensitivity and resolution.

[0007] Therefore, an object of the present invention is to provide a curable composition that has excellent sensitivity and resolution even when subjected to a heat treatment at a high temperature before exposure. Another object of the present invention is to provide a method for producing a pixel, a film, a solid-state imaging device, an image display device, and a photopolymerization initiator.

[0008] The present inventors have conducted research and found that the above object can be achieved by using a curable composition described below, and have thus completed the present invention.

[0009] <1> A curable composition comprising a photopolymerization initiator, a polymerizable compound, and a solvent, wherein the photopolymerization initiator comprises a compound A represented by formula (1A) or formula (1B); In formula (1A) and formula (1B), R １ａ and R １ｂ each independently represents a hydrogen atom or a monovalent organic group; R ２ａ and R ２ｂ each independently represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; X １ａ and X １ｂ are each independently O, S, or NR Ｘ１ or CR Ｘ２ R Ｘ３ represents R Ｘ１ ~R Ｘ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R Ｘ２ and R Ｘ３ may be bonded via a single bond or a divalent linking group to form a ring, and R Ｘ１ ~R Ｘ３ Either of the above and L １ａ , L １ｂ , R １ａ or R ７ｂ may be bonded via a single bond or a divalent linking group to form a ring, １ａ and L １ｂ R each independently represents a single bond or a divalent linking group; ５ａ ~R ８ａ and R ５ｂ ~R ８ｂeach independently represents a hydrogen atom or a substituent, ５ａ ~R ８ａ two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ａ and R ５ａ may be bonded to each other via a single bond or a divalent linking group to form a ring, and R ５ｂ ~R ７ｂ two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ｂ and R ５ｂ may be bonded to each other via a single bond or a divalent linking group to form a ring, and R １ｂ and R ８ｂ may be bonded via a single bond or a divalent linking group to form a ring, and n represents 0 or 1. <2> L in the above formula (1A) １ａ and L of formula (1B) １ｂ <3> The curable composition according to <1>, wherein R in the formula (1A) is independently a single bond or an alkylene group. １ａ and R of formula (1B) １ｂ each independently represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and the substituent is an alkyl group, an aryl group, a heteroaryl group, -OR ２０１ , -SR ２０１ , -COR ２０１ , -SO ２ R 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, or a halogen atom; R ２０１ ~R ２０５<4> The curable composition according to <1> or <2>, wherein R in the formula (1A) represents a monovalent organic group. １ａ and R of formula (1B) １ｂ are each independently a substituted aryl group or a substituted heteroaryl group, and the substituent of the aryl group or heteroaryl group is —COR ２０１ or -SO ２ R ２０１ and R ２０１ represents an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, and the substituent which the aromatic ring group or the heterocyclic group may have is an alkyl group, an aryl group, a heteroaryl group, -OR ３０１ , -SR ３０１ , -COR ３０１ , -SO ２ R 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, or a halogen atom; R ３０１ ~R ３０５ each independently represent a monovalent organic group. <5> The curable composition according to <1> or <2>, wherein the compound A is a compound represented by formula (4): In formula (4), R ４２ represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; L ４ represents a single bond or an alkylene group having 1 to 4 carbon atoms; R ４５ ~R ４８ each independently represents a hydrogen atom or a substituent, ４５ ~R ４８two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ４９ represents an alkyl group, an aryl group, or a halogen atom, and when k is 2 or more, a plurality of R ４９ may be the same or different, and multiple R ４９ two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ５０ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -OR ５０１ , -SR ５０１ , -COR ５０１ , -SO ２ R ５０１ , -NR ５０２ R ５０３ , -CONR ５０２ R ５０３ , -NR ５０４ COR ５０５ , -OCOR ５０１ , -COOR ５０１ , -SCOR ５０１ , -OCSR ５０１ , -COSR ５０１ , -CSOR ５０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ５０１ ~R ５０５ each independently represents a monovalent organic group; ５１ and R ５２ each independently represents a hydrogen atom or an alkyl group, R ５１ and R ５２ may be bonded via a single bond or a divalent linking group to form a ring, R ４９ is R ４５ or R ５１ may be bonded to R via a single bond or a divalent linking group to form a ring, ４９ and R ５０ may be bonded via a single bond or a divalent linking group to form a ring, R ５２ and L ４may be bonded via a single bond or a divalent linking group to form a ring, and k represents an integer of 0 to 4. <6> The curable composition according to <1> or <2>, wherein the photopolymerization initiator further comprises a photopolymerization initiator other than Compound A. <7> The curable composition according to <1> or <2>, wherein the photopolymerization initiator further comprises a photopolymerization initiator other than Compound A. <8> The curable composition according to <1> or <2>, wherein the photopolymerization initiator further comprises an amine compound. <9> The curable composition according to <1> or <2>, wherein the photopolymerization initiator further comprises a chain transfer agent. <10> The curable composition according to <1> or <2>, wherein the photopolymerization initiator further comprises a resin. <11> The curable composition according to <10>, wherein the resin comprises a resin having a crosslinkable group. <12> A method for manufacturing a pixel, comprising: forming a curable composition layer on a support using the curable composition according to <1> or <2>; irradiating the curable composition layer with light having a wavelength of 150 to 300 nm to expose it in a pattern; and developing and removing the unexposed areas of the curable composition layer. <13> A film obtained by curing the curable composition according to <1> or <2>. <14> A solid-state imaging device comprising the film according to <13>. <15> An image display device comprising the film according to <13>. <16> A photopolymerization initiator comprising a compound represented by formula (1A) or formula (1B); In formula (1A) and formula (1B), R １ａ and R １ｂ each independently represents a hydrogen atom or a monovalent organic group; R ２ａ and R ２ｂ each independently represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; X １ａ and X １ｂ are each independently O, S, or NR Ｘ１ or CR Ｘ２ R Ｘ３ represents R Ｘ１ ~R Ｘ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R Ｘ２ and R Ｘ３ may be bonded via a single bond or a divalent linking group to form a ring, and R Ｘ１ ~R Ｘ３ Either of the above and L１ａ , L １ｂ , R １ａ or R ７ｂ may be bonded to each other via a single bond or a divalent linking group to form a ring, and L １ａ and L １ｂ R each independently represents a single bond or a divalent linking group; ５ａ ~R ８ａ and R ５ｂ ~R ８ｂ each independently represents a hydrogen atom or a substituent, ５ａ ~R ８ａ two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ａ and R ５ａ may be bonded to each other via a single bond or a divalent linking group to form a ring, and R ５ｂ ~R ７ｂ two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ｂ and R ５ｂ may be bonded to each other via a single bond or a divalent linking group to form a ring, and R １ｂ and R ８ｂ may be bonded via a single bond or a divalent linking group to form a ring; n represents 0 or 1.

[0010] According to the present invention, it is possible to provide a curable composition having excellent sensitivity and resolution even when subjected to a heat treatment at a high temperature before exposure. The present invention also provides a pixel manufacturing method, a film, a solid-state imaging device, an image display device, and a photopolymerization initiator.

[0011] The present invention will be described in detail below. In this specification, the term "to" is used to mean that the numerical values ​​before and after the term are included as the lower and upper limits. In the description of groups (atomic groups) in this specification, a term without specifying whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (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. As used herein, "(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 the structural formulae herein, Me refers to a methyl group, Et refers to an ethyl group, Bu refers to a butyl group, and Ph refers to a phenyl group. As used herein, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography). As used herein, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. As used herein, the term "pigment" refers to a coloring material that is difficult to dissolve in a solvent. As used herein, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.

[0012] <Curable Composition> The curable composition of the present invention includes a photopolymerization initiator, a polymerizable compound, and a solvent, and is characterized in that the photopolymerization initiator includes a compound A represented by formula (1A) or formula (1B).

[0013] The curable composition of the present invention exhibits excellent sensitivity and resolution even when subjected to a heat treatment at a high temperature before exposure. The reason for this effect is presumed to be as follows. According to the inventors' investigations, it was found that Compound A is a highly crystalline compound. It is presumed that this compound has high crystallinity because it has a structure in which an indole ring and a cyclic oxime moiety of a cyclic structure formed by containing an oxime group are condensed. Since the curable composition of the present invention uses such a highly crystalline compound as a photopolymerization initiator, decomposition of the compound can be suppressed even when heat treatment is performed at a temperature exceeding 100°C (e.g., 140°C). Therefore, the curable composition of the present invention exhibits excellent sensitivity and resolution even when heat treatment is performed at a high temperature before exposure.

[0014] In addition, since the curable composition of the present invention can be heat-treated at a high temperature before exposure, the solvent can be sufficiently removed from the film, and the resolution can be further improved. Furthermore, even when a solvent with a high boiling point is used, the solvent can be sufficiently removed from the film by heat treatment before exposure. Therefore, a solvent with a high boiling point can also be used.

[0015] According to the curable composition of the present invention, the polymerization reaction can be sufficiently promoted even at the bottom (support side) of the film by exposure, so that a film having excellent adhesion to the support can be formed.

[0016] The curable composition of the present invention preferably further contains a colorant. The curable composition containing a colorant is preferably used as a curable 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.

[0017] 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 curable composition containing a chromatic colorant.

[0018] 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 curable composition containing an infrared-absorbing colorant.

[0019] 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. Examples of the infrared transmission filter include a filter that satisfies 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 that has 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.

[0020] The curable composition of the present invention can also be used as a light-shielding film.

[0021] The solids concentration of the curable 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.

[0022] The curable composition of the present invention exhibits high sensitivity when exposed to light with a wavelength of 150 to 300 nm. Therefore, the curable composition of the present invention is preferably used as a curable composition for exposure to light with a wavelength of 150 to 300 nm. Examples of light with 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 with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm.

[0023] Each component used in the curable composition of the present invention will be described below.

[0024] <<Photopolymerization Initiator>> The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0025] (Specific Compound) The curable composition of the present invention contains a compound A represented by formula (1A) or (1B) as a photopolymerization initiator. Hereinafter, the compound A is also referred to as a specific compound.

[0026] -R １ａ and R １ｂ R of formula (1A) １ａ and R of formula (1B) １ｂ are each independently 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.

[0027] 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.

[0028] The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.

[0029] The number of carbon atoms constituting the ring of the heteroaryl group is preferably 1 to 15, and 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, and more preferably 1 or 2. The heteroaryl group may be a monocyclic ring or a fused ring.

[0030] The acyl group is —COR ２０１ It is preferable that the group is a group represented by the following formula:

[0031] 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 an —OR ２０１ , -SR ２０１ , -COR ２０１ , -SO ２ R 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 -SO ２ R ２０１ Preferably, -COR ２０１ It is more preferable that R ２０１~R ２０５ each independently represents a monovalent organic group.

[0032] R ２０１ ~R ２０５ Examples 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. ２０１ ~R ２０５ 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. ２０１ ~R ２０５ The number of carbon atoms in the aromatic ring group represented by R 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. 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.

[0033] 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 them, 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 the aromatic ring group or heterocyclic group 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 above-mentioned substituents. Examples of the aromatic ring group or heterocyclic group having three or more fused rings include the following groups:

[0034]

[0035] In the above formula, * represents a bond, R ａ１ ~R ａ３２each independently represents a substituent, R ａｒ１ ~R ａｒ２５ each independently represents a hydrogen atom, an alkyl group, or an aryl group, and 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.

[0036] The above R ２０１ ~R ２０５ The alkyl group, aromatic ring group and heterocyclic group represented by may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, -OR ３０１ , -SR ３０１ , -COR ３０１ , -SO ２ R 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 , -SO ２ R ３０１ , -NR ３０２ R ３０３ or a nitro group, and —COR ３０１ or -SO ２ R ３０１ More preferably, -COR ３０１ It is more preferable that R ３０１ ~R ３０５ R each independently represents a monovalent organic group. ３０１ ~R ３０５Examples 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.

[0037] R in formula (1A) １ａ and R of formula (1B) １ｂ are each independently 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 -SO ２ R 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.

[0038] R in formula (1A) １ａ and R of formula (1B) １ｂ is preferably a group represented by formula (Az-1). In formula (Az-1), * represents a bond, and Rz １ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -ORz １０１ , -SRz １０１ , -CORz １０１ , -SO ２ Rz １０１ , -NRz １０２ Rz １０３ , -CONRz １０２ Rz １０３ , -NRz １０４ CORz １０５ , -OCORz １０１ , -COORz １０１ , -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; 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, and when p is 2 or more, a plurality of Rz ２ may be the same or different, and a plurality of Rz ２ Two of these may be bonded via a single bond or a divalent linking group to form a ring.

[0039] Rz in formula (Az-1) １ is a hydrogen atom, -CORz １０１ or -SO ２ Rz １０１ Preferably, -CORz １０１ or -SO ２ Rz １０１ More preferably, -CORz １０１ It is more preferable that:

[0040] 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. 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 the formula (I) include the alkyl group, aromatic ring group and heterocyclic group shown above.

[0041] In formula (Az-1), p represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0042] Rz １ and Rz ２ may be bonded via a single bond or a divalent linking group to form a ring. When p is 2 or more, a plurality of Rz ２may be the same or different, and a plurality of Rz ２ Two of the groups may be bonded to each other via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include -O-, -S-, -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ -, -CR Ｌ４ =CR Ｌ５ -CR Ｌ６ =CR Ｌ７ - is mentioned. 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, even 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 an aromatic ring or a non-aromatic ring.

[0043] -R ２ａ and R ２ｂ R of formula (1A) ２ａ and R of formula (1B) ２ｂ each independently represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group, and is preferably an alkyl group or an aryl group, more preferably an alkyl group.

[0044] R in formula (1A) ２ａ and R of formula (1B) ２ｂThe 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. The alkyl group is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group.

[0045] R in formula (1A) ２ａ and R of formula (1B) ２ｂ The number of carbon atoms in the alkoxy 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 alkoxy group is preferably linear or branched, more preferably linear. The alkoxy group may have a substituent, but is preferably unsubstituted.

[0046] R in formula (1A) ２ａ and R of formula (1B) ２ｂ The number of carbon atoms in the aryl group and aryloxy group represented by the formula (I) 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.

[0047] R in formula (1A) ２ａ and R of formula (1B) ２ｂ The heteroaryl group and heteroaryloxy group represented by the formula (I) preferably have 1 to 15 carbon atoms constituting the ring, and more preferably 1 to 10. The types of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3, and more preferably 1 or 2. The heteroaryl group and heteroaryloxy group may be a monocyclic ring or a fused ring. The heteroaryl group and heteroaryloxy group may have a substituent.

[0048] -X １ａ and X １ｂ - X in formula (1A) １ａ and X in formula (1B) １ｂ are each independently O, S, or NR Ｘ１ or CR Ｘ２ R Ｘ３ represents R Ｘ１ ~R Ｘ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group.

[0049] X in formula (1A) １ａ and X in formula (1B) １ｂ is preferred for its synthesis suitability, stability in the presence of an acid or a base, and ability to inhibit yellowing of the compound. Ｘ２ R Ｘ３ It is preferable that:

[0050] R Ｘ１ ~R Ｘ３ 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. Ｘ２ and R Ｘ３ may be bonded via a single bond or a divalent linking group to form a ring. Ｘ１ ~R Ｘ３ Either of the above and L １ａ , L １ｂ , R １ａ or R ７ｂ 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—, —NR Ｌ１ -, -CR Ｌ２ R Ｌ３ -, -CR Ｌ４ =CR Ｌ５ -CR Ｌ６ =CR Ｌ７ - is mentioned. 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 Ｌ７The 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, even 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- to 7-membered ring, and even more preferably a 5- or 6-membered ring. The ring formed may be an aromatic ring or a non-aromatic ring. A non-aromatic ring is preferred.

[0051] -L １ａ and L １ｂ - L of formula (1A) １ａ and L of formula (1B) １ｂ each independently represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group. The alkylene group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkylene group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2.

[0052] -R ５ａ ~R ８ａ and R ５ｂ ~R ８ｂ - R of formula (1A) ５ａ ~R ８ａ and R of formula (1B) ５ｂ ~R ８ｂ each independently represents a hydrogen atom or a substituent, such as an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group, a nitro group, a cyano group, or a halogen atom.

[0053] R in formula (1A) ５ａ ~R ８ａ and R of formula (1B) ５ｂ ~R ８ｂare each preferably independently a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0054] In formula (1A), R ５ａ ~R ８ａ two adjacent ones of R may be bonded via a single bond or a divalent linking group to form a ring, １ａ and R ５ａ may be bonded via a single bond or a divalent linking group to form a ring. ５ｂ ~R ７ｂ two adjacent ones of R may be bonded via a single bond or a divalent linking group to form a ring, １ｂ and R ５ｂ may be bonded via a single bond or a divalent linking group to form a ring, and R １ｂ and R ８ｂ 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—, —NR Ｌ１ -, -CR Ｌ２ R Ｌ３ -, -CR Ｌ４ =CR Ｌ５ -CR Ｌ６ =CR Ｌ７ - is mentioned. 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, even 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 an aromatic ring or a non-aromatic ring.

[0055] n in formula (1A) and n in formula (1B) each independently represent 0 or 1, and preferably 1. When n is 1, the hydrolysis resistance of the compound can be improved, so that R in formula (1A) ２ａ and R of formula (1B) ２ｂ are each preferably independently a methyl group, a branched alkyl group, or an aryl group, and more preferably a methyl group, a branched alkyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0056] The specific compound is preferably a compound represented by formula (1A), and more preferably a compound represented by formula (4), because the effects of the present invention are more significantly exhibited.

[0057] In formula (4), R ４２ represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; L ４ represents a single bond or an alkylene group having 1 to 4 carbon atoms; R ４５ ~R ４８ each independently represents a hydrogen atom or a substituent, ４５ ~R ４８ two adjacent ones of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ４９ represents an alkyl group, an aryl group, or a halogen atom, and when k is 2 or more, a plurality of R ４９ may be the same or different, and multiple R ４９ two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ５０ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -OR ５０１ , -SR ５０１ , -COR ５０１ , -SO ２ R ５０１ , -NR ５０２ R ５０３ , -CONR ５０２ R ５０３ , -NR５０４ COR ５０５ , -OCOR ５０１ , -COOR ５０１ , -SCOR ５０１ , -OCSR ５０１ , -COSR ５０１ , -CSOR ５０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ５０１ ~R ５０５ each independently represents a monovalent organic group; ５１ and R ５２ each independently represents a hydrogen atom or an alkyl group, R ５１ and R ５２ may be bonded via a single bond or a divalent linking group to form a ring, R ４９ is R ４５ or R ５１ may be bonded to R via a single bond or a divalent linking group to form a ring, ４９ and R ５０ may be bonded via a single bond or a divalent linking group to form a ring, R ５２ and L ４ may be bonded via a single bond or a divalent linking group to form a ring; k represents an integer of 0 to 4.

[0058] R in formula (4) ４２ is R in formula (1A). ２ａ The same applies to the preferred range.

[0059] R in formula (4) ４５ ~R ４８ is R in formula (1A). ５ａ ~R ８ａ The same applies to the preferred range.

[0060] R ４５ ~R ４８ Two adjacent ones of these may be bonded to each other via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include -O-, -S-, -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ -, -CR Ｌ４ =CR Ｌ５ -CR Ｌ６=CR Ｌ７ - is mentioned. 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, even 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 an aromatic ring or a non-aromatic ring.

[0061] L in formula (4) ４ represents a single bond or an alkylene group having 1 to 4 carbon atoms. The alkylene group is preferably linear or branched, and more preferably linear. The alkylene group preferably has 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms.

[0062] R in formula (4) ４９ represents an alkyl group, an aryl group, or a halogen atom. When k is 2 or more, a plurality of R ４９ may be the same or different, and multiple R ４９ Two of the may be bonded via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include those mentioned above. The ring formed is preferably a 3- to 7-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring. The ring formed may be an aromatic ring or a non-aromatic ring. A non-aromatic ring is preferred.

[0063] R in formula (4) ５０ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -OR５０１ , -SR ５０１ , -COR ５０１ , -SO ２ R ５０１ , -NR ５０２ R ５０３ , -CONR ５０２ R ５０３ , -NR ５０４ COR ５０５ , -OCOR ５０１ , -COOR ５０１ , -SCOR ５０１ , -OCSR ５０１ , -COSR ５０１ , -CSOR ５０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ５０１ ~R ５０５ each independently represents a monovalent organic group.

[0064] R ５０ represents a hydrogen atom, -COR ５０１ or -SO ２ R ５０１ Preferably, -COR ５０１ or -SO ２ R ５０１ More preferably, -COR ５０１ It is more preferable that:

[0065] R ５０１ ~R ５０５ Examples of the monovalent organic group represented by R include an alkyl group, an aromatic ring group, and a heterocyclic group. ５０１ ~R ５０５ 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.

[0066] R in formula (4) ５１ and R ５２ each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom.

[0067] In formula (4), k represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0068] In formula (4), R ５１ and R ５２ may be bonded via a single bond or a divalent linking group to form a ring, R ４９ is R ４５ or R ５１ may be bonded to R via a single bond or a divalent linking group to form a ring, ４９ and R ５０ may be bonded via a single bond or a divalent linking group to form a ring, R ５２ and L ４ may be bonded via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include those mentioned above. The ring formed is preferably a 3- to 7-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring. The ring formed may be an aromatic ring or a non-aromatic ring. A non-aromatic ring is preferred.

[0069] 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.

[0070] From the viewpoint of sensitivity, the molar absorption coefficient of the 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 preferably, 20,000 L mol or more －１ ・cm －１ More preferably, 30,000 L mol or more －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 From the viewpoint of sensitivity, the molar absorption coefficient of the specific compound at a wavelength of 365 nm is preferably 500 L mol －１ ・cm －１ More than 1000 L mol is preferred.－１ ・cm －１ More preferably, 2000 L mol or more －１ ・cm －１ More preferably, 3000 L mol or more －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 The specific compound has a long-wavelength absorption end (molar absorption coefficient of 100 L mol －１ ・cm －１ The longest wavelength (the wavelength at which the absorption peak is shorter than the longest wavelength) is preferably 450 nm or less, more preferably 400 nm or less, and even more preferably 380 nm or less. 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 yellow color.

[0071] The molar absorption coefficient of a specific compound is measured by the following method: 12.5 mg of the specific compound is weighed out and placed in a 100 mL volumetric flask. Acetonitrile is added to this and completely dissolved. 2 mL of this solution is taken with a volumetric pipette and made up to a 25 mL volumetric flask. This is the measurement sample. The measurement sample is placed in a 5 mL quartz glass cell, 1 cm square, and the absorbance is measured in air to calculate the molar absorption coefficient. Examples of measurement devices include an ultraviolet-visible-near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation).

[0072] 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.

[0073] The method for producing the specific compound of the present invention is not particularly limited, and the compound may be produced by a known method or may be produced by referring to a known method. The compound can be produced by a general method for synthesizing oxime esters or ketoxime esters. For specific production methods, reference can be made to JP-A-2012-519191, which uses hydroxylamine hydrochloride, and JP-A-2012-526185, which uses isoamyl nitrite. Furthermore, for the oximation and ketoximation of cyclic ketones, reference can also be made to the methods described in JP-A-2010-032985 and JP-A-2010-185072. A general synthesis scheme is described below, but the method for producing the specific compound is not limited thereto. In the structural formula shown below, Ms is a mesyl group.

[0074] When a compound having multiple carbonyl groups in one molecule is used as intermediate (I), 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.

[0075] The curable composition of the present invention may contain an oxime body as a precursor and a ketone body (intermediate (I)) before oximation. When these are contained, the content of each of the oxime body and the ketone body (intermediate (I)) 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.

[0076] Specific examples of the specific compound include compounds A-1 to A-174 shown below.

[0077] The curable composition of the present invention may use only one of the specific compounds described above, or two or more of them in combination. By using two or more of them in combination, an effect of achieving a better balance between resolution and sensitivity can be obtained, regardless of whether the exposure light source is KrF line or i-line.

[0078] The impurities that may be contained in the specific compound are 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, 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. The content of organic solvent 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. 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, 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 acids include formic acid, acetic acid, propionic acid, succinic acid, and phthalic 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, 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 bases include triethylamine, dimethylamine, diethylamine, piperidine, pyrrolidine, morpholine, and amines used in the production of 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 halogens 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 weight of the specific compound. It is even more preferable that the content is less than 0.0001 parts by mass, and particularly preferably 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.

[0079] (Other Photopolymerization Initiators) The curable 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 and the other photopolymerization initiator are used in combination, 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, and more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 50 parts by mass or more.

[0080] Examples of the other photopolymerization initiator 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 initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, or an acylphosphine compound, even more preferably an α-aminoketone compound or an oxime compound, and particularly preferably an oxime compound.

[0081] Other photopolymerization initiators include the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, the compounds described in Japanese Patent No. 6301489, and the compounds described in MATERIAL STAGE 37-60pp, vol. 19, No. 3,peroxide-based photopolymerization initiators described in WO 2019, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, 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, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992 A, oxime-based photopolymerization initiators described in JP-A-2020-172619, polymers described in JP-A-2020-172619, compounds represented by formula 1 described in WO 2020 / 152120, compounds described in JP-A-2021-181406, photopolymerization initiators described in JP-A-2022-013379, compounds represented by formula (1) described in JP-A-2022-015747, fluorine-containing fluorene oxime ester-based photoinitiators described in JP-T-2021-507058, and those described in Chinese Patent Application Publication No. 110764367. Initiators described in JP-A-2022-518535, initiators described in WO 2021 / 175855, compounds described in Taiwan Patent Application 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 Application Publication No. 110066225, Korean Patent Publication No. 10-2022-0076157 Compounds described in WO 2019 / 013112, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 0062, oxime ester photopolymerization initiators described in Japanese Patent 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, initiators described in JP 2022-515524, initiators described in JP 2023-517304, initiators described in Chinese Patent Publication No. 114149517, and the like.

[0082] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0083] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.

[0084] Examples of the oxime compound include the compounds described in paragraph 0142 of WO 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by the general formula (1) of JP-A-2021-173858, and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) of JP-A-2021-170089 and the compounds described in paragraphs 0117 to 0120. Specific examples of the oxime compound 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 OXE05, Irgacure OXE06, Irgacure OXE07, Irgacure OXE08, Irgacure OXE09, Irgacure OXE10, Irgacure OXE11, Irgacure OXE12, Irgacure OXE13, Irgacure OXE14, Irgacure OXE15, Irgacure OXE16, Irgacure OXE17, Irgacure OXE18, Irgacure OXE19, Irgacure OXE20, Irgacure OXE21, Irgacure OXE22, Irgacure OXE23, Irgacure OXE24, Irgacure OXE25, Irgacure OXE26, Irgacure OXE27, Irgacure OXE28, Irgacure OX OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples of the oxime compound include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (all manufactured by TRONLY Corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). In addition, 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).

[0085] 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.

[0086] As another photopolymerization initiator, a compound represented by formula (OX-1) can also be used.

[0087] 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; 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, and n represents 0 or 1.

[0088] X in formula (OX-1) １ａ Examples 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 via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group. Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - and groups combining these. ｘrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0089] 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).

[0090] In the formula R 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.

[0091] 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.

[0092] R Ｘ１ ~R Ｘ９ The 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.

[0093] 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.

[0094] R Ｘ１ ~R Ｘ９The 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.

[0095] 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 atoms, nitrogen atoms, and 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.

[0096] R in formula (OX-1) １ａ represents a hydrogen atom or an acyl group, and is preferably an acyl group.

[0097] 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. ２ａ 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 ２ａ The alkyl group represented by R is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. 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.

[0098] R in formula (OX-1) ３ａ and R ４ａR each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. 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.

[0099] Alk of formula (OX-1) １ and Alk ２ each 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.

[0100] In formula (OX-1), n ​​represents 0 or 1, and is preferably 0.

[0101] 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.

[0102] As another photopolymerization initiator, a compound represented by formula (OX-2) can also be used.

[0103]

[0104] 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, Ar １ｂ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent; n represents 0 or 1;

[0105] 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 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.

[0106] R ３ｂ ~R ７ｂ Examples of the substituent represented by R include a halogen atom, an alkyl group, and an aryl group. Examples of the alkyl group and the aryl group include those described above. ３ｂ ~R ７ｂ is preferably a hydrogen atom.

[0107] Ar １ｂ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, Ar １ｂis 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.

[0108] As another photopolymerization initiator, a compound represented by formula (OX-3) can also be used.

[0109]

[0110] 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; 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; １ｃ Ha-CH ２ represents -, -N-, -O- or -S-; k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.

[0111] R １ｃ and R ２ｃExamples 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 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group. R ２ｃ is preferably an alkyl group having a branched or cyclic structure.

[0112] R ３ｃ Examples 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.

[0113] 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 group and aryl group in R １ｃ and R ２ｃ When k is 1, L １ｃ is preferably a single bond.

[0114] X １ｃ is -CH ２ It represents -, -N-, -O- or -S-, and is preferably -O- or -S-.

[0115] Ar １ｃrepresents 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.

[0116] 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.

[0117] k represents 0 or 1, and is preferably 0. m represents an integer of 0 to 4, and is preferably 0 or 1, and more preferably 1. n represents 0 or 1, and is preferably 0.

[0118] Specific examples of the oxime compound include the compounds shown below.

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] As the other photopolymerization initiator, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used. Specific examples of the bifunctional or trifunctional or higher functional photopolymerization initiator include the compounds described in paragraph 0148 of WO 2022 / 065215.

[0125] The content of the photopolymerization initiator in the total solid content of the curable 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 curable 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.

[0126] 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.

[0127] The content of the specific compound in the total solid content of the curable 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 curable 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, it is preferable that the total amount thereof is in the above range.

[0128] <<Polymerizable Compound>> The curable 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.

[0129] The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but 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.

[0130] The ethylenically unsaturated bond-containing group value (hereinafter referred to as C═C value) of the polymerizable compound is preferably 2 to 14 mmol / g from the viewpoint of storage stability of the curable composition. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and even more preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less. The C═C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

[0131] The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a trifunctional to 15-functional (meth)acrylate compound, and more preferably a trifunctional 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.

[0132] 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 having a structure in which the (meth)acryloyl group is bonded via an ethylene glycol and / or propylene glycol residue (e.g., SR454, 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.), and 1,6-hexanediol diacrylate (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). HDDA), 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 Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-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 having an acidic group), Etercure 6361-100 (Eternal Materials, polymerizable compound having a hyperbranched structure), EBECRYL80 (amine-containing tetrafunctional monomer, manufactured by Daicel-Olknes Co., Ltd.), EBECRYL7100 (amine-containing bifunctional monomer, manufactured by Daicel-Olknes Co., Ltd.), CN371NS (amine-containing bifunctional monomer, 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-A No. 2023-043479, and polymerizable compounds described in JP-A No. 2023-529984 can also be used.

[0133] As the polymerizable compound, a polymerizable compound having an ethylene oxide repeating chain can also be used. According to this embodiment, the effects of the present invention are more significantly exhibited. Examples of the polymerizable compound having an ethylene oxide repeating chain include a compound represented by formula (EO-1).

[0134] R in formula (EO-1) Ｅ１ represents a hydrogen atom or a methyl group.

[0135] L in formula (EO-1) Ｅ１ represents an m-valent linking group. Ｅ１ The m-valent linking group represented by is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR Ａ１ -, -CO-, -COO-, -OCO-, -SO ２ - 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.

[0136] 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.

[0137] 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 the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr):

[0138] In the formula, * represents a bond, and R ｆ１ and R ｆ２ each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R ｆ１ may be the same or different, and m R ｆ１ Two of the R ｆ１ When n is 2 or more, n R ｆ２ may be the same or different, and n R ｆ２ Two of the R ｆ２ They may be bonded to each other to form a ring. ｆ１ and R ｆ２ The substituent represented by is a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR ｆ１１ , -COR ｆ１２ , -COOR ｆ１３ , -OCOR ｆ１４ , -NR ｆ１５ R ｆ１６ , -NHCOR ｆ１７ , -CONR ｆ１８ R ｆ１９ , -NHCONR ｆ２０ R ｆ２１ , -NHCOOR ｆ２２ , -SR ｆ２３ , -SO ２ R ｆ２４ , -SO ２ OR ｆ２５ , -NHSO ２ R ｆ２６ or -SO ２ NR ｆ２７ R ｆ２８ Examples include: ｆ１１ ~R ｆ２８ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0139] Specific examples of polymerizable compounds having a fluorene skeleton include compounds having the following structure: Furthermore, 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).

[0140] The content of the polymerizable compound in the total solid content of the curable 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 curable composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types of polymerizable compounds are contained, the total amount thereof is preferably within the above range.

[0141] <<Resin>> The curable composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing pigments and the like in the curable composition or for the purpose of using as a binder. Note that a resin used mainly for dispersing pigments and the like in the curable composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can also be used for purposes other than these uses.

[0142] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0143] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. 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, and the resins described in paragraphs 0199 to 0233 of JP 2020-186373 A. Resins described above, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, copolymers containing epoxy groups and acid groups described in WO 2022 / 030445 A, 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 can also be used.

[0144] 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.

[0145] The acid value of the resin having acid groups is preferably 30 to 500 mgKOH / g. The lower limit is preferably 40 mgKOH / g or more, and more preferably 50 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

[0146] 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 the 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.

[0147] For resins having acid groups, please refer to the descriptions in 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. Alternatively, commercially available resins having acid groups can 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. Furthermore, examples of methods for introducing acid groups into the resin include a method in which an acid anhydride is reacted with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce the acid group.

[0148] The curable 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 containing 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 containing 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.

[0149] 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 The Lubrizol Group, 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-A-2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A-2018-156021, or the vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein by reference.

[0150] The curable composition of the present invention also preferably contains both a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the curable composition can be further improved. 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.

[0151] 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 the 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 the 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.

[0152] It is also preferable to use a resin having a crosslinkable group as the resin. Examples of the crosslinkable group include a (meth)acryloyl group, an epoxy group, and an oxetanyl group. When a resin having a crosslinkable group is used, the content of the resin having a crosslinkable group in the resin contained in the curable composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0153] The curable 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. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more is preferred, assuming that the total amount of acid groups and basic groups is 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. 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. As the basic dispersant (basic resin), a resin in which the amount of basic groups is greater than 50 mol% is preferred, assuming that the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

[0154] The resin used as the dispersant is preferably a graft resin. For details of the graft resin, please refer to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[0155] The resin used as the dispersant is preferably a resin having an aromatic carboxy group, such as those mentioned above.

[0156] 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 containing 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.

[0157] 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-A-2013-043962.

[0158] 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.

[0159] 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, 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, and the like can also be used.

[0160] Dispersants are also available as commercially available products, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Japan, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. 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.

[0161] The content of the resin in the total solid content of the curable 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, and more preferably 40% by mass or less. The content of the resin having an acid group in the total solid content of the curable 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, and more preferably 40% by mass or less.

[0162] The content of the resin is preferably 100 to 1,000 parts by mass per 100 parts by mass of the polymerizable compound. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 600 parts by mass or less, and more preferably 500 parts by mass or less. The curable composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more types of resins are contained, the total amount thereof preferably falls within the above range.

[0163] <<Colorant>> The curable composition of the present invention preferably contains a colorant. Examples of the colorant include a white colorant, a black colorant, a chromatic colorant, and an infrared-absorbing colorant. In the present invention, the white colorant includes not only pure white colorants but also light gray colorants close to white (for example, grayish white, light gray, etc.).

[0164] 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.

[0165] 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.

[0166] 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.

[0167] The specific surface area of ​​the pigment is 1 to 300 m ２ / g. The lower limit is 10 m ２ / g or more, and ２ / g or more is more preferable. ２ / g or less, and ２ The value of the specific surface area 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.

[0168] (Chromatic Colorant) 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.

[0169] Examples of the red colorant include a diketopyrrolopyrrole compound, an anthraquinone compound, an azo compound, a naphthol compound, an azomethine compound, a xanthene compound, a quinacridone compound, a perylene compound, and a thioindigo compound, and the like, preferably a diketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound, and more preferably a diketopyrrolopyrrole compound. The red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0170] Specific examples of red colorants include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, Examples of red pigments include 150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294,295,296,297. In addition, as a red colorant, a compound described in paragraph number 0034 of WO 2022 / 085485, or a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

[0171] As the red colorant, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.

[0172] Examples of the green colorant include phthalocyanine compounds and squarylium compounds, and the phthalocyanine compounds are preferred. The green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0173] Specific examples of green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, halogenated zinc phthalocyanine pigments 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 the compounds described in WO 2015 / 118720. Furthermore, compounds described in paragraph 0029 of WO 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.

[0174] As the green colorant, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred.

[0175] 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 orange pigments such as C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0176] 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 the yellow colorant include C.I. 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, 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.

[0177] As the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used.

[0178] As the yellow colorant, the compounds described in paragraphs 0031 to 0033 of WO 2022 / 085485, the methine dyes described in JP-A 2019-073695, and the methine dyes described in JP-A 2019-073696 can be used.

[0179] Examples of the purple colorant include an oxazine compound, a quinacridone compound, a perylene compound, and an indigo compound, and the oxazine compound is preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of the purple colorant include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0180] 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 blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, 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.

[0181] 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.

[0182] A dye polymer can also be used as a chromatic colorant. The dye polymer is preferably a dye dissolved in a solvent when used. The dye polymer may also form particles. When the dye polymer is particulate, it is typically used in a dispersed state in a solvent. A particulate dye polymer can be obtained, for example, by emulsion polymerization, and specific examples of the compounds and production methods described in JP-A 2015-214682 include those described in JP-A 2015-214682. The dye polymer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight-average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. As the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016 / 031442, etc. can also be used.

[0183] As chromatic colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638 A, phthalocyanine compounds described in WO 2020 / 174991 A, isoindoline compounds described in JP 2020-160279 A or salts thereof, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A Compounds represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in JP-A-2020-180176, phenothiazine compounds described in JP-A-2021-187913, halogenated zinc phthalocyanines described in WO 2022 / 004261, and halogenated zinc phthalocyanines described in WO 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-A-2022-029701, isoindoline compounds described in WO 2022 / 014635, aluminum phthalocyanine compounds described in WO 2022 / 024926, and JP-A-2022-045 Compounds described in Patent Publication No. 895, compounds described in WO 2022 / 050051, compounds described in JP 2020-090676, compounds described in JP 2020-055956, compounds described in JP 2021-031681, compounds described in JP 2022-056354, compounds described in US 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 Application Publication No. 113881244 A, compounds described in Chinese Patent Application Publication No. 113881245 A, compounds described in Chinese Patent Application Publication No. 113881246 A, compounds described in JP 2022-104822 A, compounds described in JP 2022-096701 A, compounds described in JP 2020- Compounds described in JP-A-023652, green pigments described on pages 80 to 84 of the Journal of the Color Materials Association (published in 2022), compounds described in JP-A-2022-143135, compounds described in JP-A-2022-140287, compounds described in WO 2022 / 136308, perylene compounds described in Chinese Patent Application Publication No. 113061349, cyan pigments described in Korean Patent Publication No. 10-2017-0018993, isoindoline compounds described in JP-A-2020-180176, Compounds described in JP-A-3-013209, compounds described in JP-A-2023-013166, xanthene compounds described in WO 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, JP-A-2023-05 Compounds described in JP-A-6463, compounds described in JP-T-2023-515473, dioxane compounds described in JP-T-2022-549530, pigment preparations described in JP-A-2022-061494, diketopyrrolopyrrole pigments described in JP-A-2023-057917, diketopyrrolopyrrole compounds described in JP-A-2023-061273, phthalocyanines described in JP-T-2023-519314, and quinophthalones described in JP-A-2023-080419 can also be used.

[0184] Two or more chromatic colorants may be used in combination. When two or more chromatic colorants are used in combination, the combination of the two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the curable composition contains two or more chromatic colorants and exhibits a black color through the combination of the two or more chromatic colorants, the curable composition of the present invention can be preferably used as a curable composition for forming an infrared transmission filter. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant. (3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant. (4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. (5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow coloring material and a purple coloring material.

[0185] (White coloring material) Examples of the white coloring material 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. As the white coloring material, the white pigments described in paragraphs 0040 to 0043 of WO 2022 / 085485 can be used.

[0186] (Black Colorant) The black colorant is not particularly limited, and known materials can be used. The black colorant may be an inorganic black colorant or an organic black colorant. The black colorant is preferably a pigment. In this specification, the black colorant refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0187] 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. As the titanium black, the titanium black described in paragraph 0044 of WO 2022 / 085485 can be used. As the inorganic black colorant, zirconium nitride powder described in JP 2023-048173 A can also be used.

[0188] 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, examples of organic black colorants include perylene black (such as Lumogen Black FK4280) described in paragraphs 0016 to 0020 of JP-A-2017-226821 and black azo pigments described in JP-A-2022-121935.

[0189] 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.

[0190] (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 ２is preferably 0.08 or less, and more preferably 0.04 or less. The infrared absorbing colorant is preferably a pigment, and more preferably an organic pigment.

[0191] 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-2023-068643, 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.

[0192] The content of the colorant in the total solid content of the curable 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.

[0193] The content of the pigment in the total solid content of the curable 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. According to the curable composition of the present invention, even when the pigment content is high, it is possible to form a film in which foreign matter defects are suppressed, and therefore, when the pigment content is high, the effects of the present invention are more pronounced.

[0194] 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.

[0195] <<Chain Transfer Agent>> The curable composition of the present invention preferably contains a chain transfer agent. According to this embodiment, it is possible to further increase the sensitivity when exposed to light having a wavelength of 150 to 300 nm, such as KrF radiation. Examples of the chain transfer agent include a thiol compound, a thiocarbonylthio compound, and a dimer of an aromatic α-methylalkenyl, 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.

[0196] 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.

[0197] The thiol compound is preferably a compound represented by the following formula (SH-1): 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.

[0198] 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-, -SO ２ - 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 fused ring. The heterocyclic group may be a monocyclic or 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. L １ The number of carbon atoms constituting the group is preferably 3 to 100, and more preferably 6 to 50.

[0199] 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.

[0200] Specific examples of thiol compounds include the compounds described in the Examples below and the compounds described in paragraphs 0100 to 0103 of WO 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Suncera M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Corporation). The thiol compounds described in JP 2020-109068 A can also be used as chain transfer agents.

[0201] The molecular weight of the chain transfer agent is preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because the SH valence per weight can be increased.

[0202] The content of the chain transfer agent in the total solid content of the curable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, and more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0203] <<Amine Compound>> The curable compound of the present invention preferably contains an amine compound. According to this embodiment, the efficiency of radical generation from the photopolymerization initiator during exposure can be further improved, and the polymerization reaction of the polymerizable compound can be further promoted.

[0204] 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.

[0205] 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 or 2 amino groups.

[0206] 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 It is preferable that the concentration is less than 100 L mol －１ ・cm －１ It is more preferable that it is less than 10 ...

[0207] The amine compound may be a primary, secondary or tertiary amine, but is preferably a tertiary amine.

[0208] 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 a combination of an alkyl group and an aryl group is most preferred.

[0209] 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.

[0210] The amine compound is preferably a compound represented by formula (B-1). 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; m represents an integer of 0 to 5;

[0211] R ａ , R ｂ and R ｃ Examples of the organic group represented by include an alkyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferred. 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 phosphate group, and a hydroxy group, and a hydroxy group is preferred. m represents an integer of 0 to 5, and is preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0212] Specific examples of the amine compound include compounds T-5 and T-6 described in the Examples below, 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, p -dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 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-diethylaminobenzal)acetone coumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholino Examples thereof include benzophenone, 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.

[0213] The content of the amine compound is preferably 5 to 1,000 parts by mass relative to 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. Only one type of amine compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof falls within the above range.

[0214] <<Acid Anhydride>> The curable composition of the present invention may contain an acid anhydride. Even if the specific compound is hydrolyzed to a free OH form, the presence of the acid anhydride allows it to be restored to a photodecompositionally active oxime compound again. This makes it possible to suppress a decrease in sensitivity over time.

[0215] 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, Examples of the anhydride include aliphatic carboxylic acid anhydrides such as 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and glutaric anhydride; aromatic carboxylic acid anhydrides such as benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride; and sulfocarboxylic acid anhydrides such as 2-sulfobenzoic anhydride.

[0216] 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.

[0217] <<Pigment Derivative>> The curable 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 colorant such as a pigment in the curable composition.

[0218] Examples of the pigment derivative include a compound 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.

[0219] 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.

[0220] 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 an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , -CONHCOR Ｘ３ or -SO ２ NHCOR Ｘ４ A group represented by the formula: ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , or -SO ２ NHCOR Ｘ４ A group represented by the formula: ２ NHSO ２ R Ｘ１ or -CONHSO ２ R 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.

[0221] 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.

[0222] The amino group is —NR ｘ１１ R ｘ１２ and a cyclic amino group.

[0223] -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.

[0224] 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.

[0225] The pigment derivative may be a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative). The maximum molar absorption coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is 3000 L mol －１ ・cm －１ It is preferable that the concentration is 1000 L mol or less. －１ ・cm －１ More preferably, it is 100 L mol or less. －１ ・cm －１ The lower limit of εmax is, for example, 1 L mol －１ ・cm －１ or more, and 10 L mol －１ ・cm －１ More than that is fine.

[0226] Specific examples of pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of WO 2022 / 085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, compounds described in JP 2019-172968 A, and compounds described in the specification of Chinese Patent Application Publication No. 115124889.

[0227] 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 curable 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.

[0228] <<Polyalkyleneimine>> The curable composition of the present invention can 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 curable 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.

[0229] 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 the boiling point elevation method is used. If the number average molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the number average molecular weight value measured by the viscosity method is used. If the number average molecular weight cannot be measured by the viscosity method or is difficult to measure, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) is used.

[0230] 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.

[0231] 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. It is particularly preferred that the polyalkyleneimine be 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.).

[0232] The content of the polyalkyleneimine in the total solid content of the curable 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, it is preferable that the total amount thereof is within the above range.

[0233] <<Solvent>> The curable composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. 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 ethylene glycol monomethyl ether acetate include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount may be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

[0234] The metal content of the organic solvent is preferably low. The metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, an organic solvent having a metal content of ppt (parts per trillion) by mass may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0235] 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.

[0236] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The organic solvent may contain only one type of isomer or multiple types of isomers.

[0237] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0238] The content of the solvent in the curable 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.

[0239] From the viewpoint of environmental regulations, it is preferable that the curable composition of the present invention is substantially free of environmentally restricted substances. In the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the curable 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, the VOC (Volatile Organic Compounds) regulations, etc., and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing the components used in the curable composition, and may be mixed into the curable composition as residual solvents. From the viewpoints of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. Examples of methods for reducing environmentally restricted substances include a method in which the system is heated or depressurized to a temperature above the boiling point of the environmentally restricted substance, thereby distilling off the environmentally restricted substance from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is useful to perform azeotropy with a solvent having a boiling point equivalent 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 prior to distillation under reduced pressure to prevent intermolecular crosslinking due to the progress of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of raw materials, the stage of a product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a curable composition prepared by mixing these compounds.

[0240] <<Compound Having a Cyclic Ether Group>> The curable composition of the present invention can 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 per molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups per molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.

[0241] Examples of compounds having a cyclic ether group include the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, 0147 to 0156 of JP-A-2014-043556, and 0085 to 0092 of JP-A-2014-089408, and the compounds described in JP-A-2017-179172, the xanthene epoxy resins described in JP-A-2021-195421, and the xanthene epoxy resins described in JP-A-2021-195422 can be used.

[0242] 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.

[0243] Commercially available examples of compounds having a cyclic ether group include 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).

[0244] The content of the compound having a cyclic ether group in the total solid content of the curable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be in the above range.

[0245] <<UV Absorber>> The curable composition of the present invention may contain an UV absorber. Examples of UV 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 WO 2022 / 085485, the reactive triazine UV absorber described in JP 2021-178918 A, the UV absorber described in JP 2022-007884 A, the compound described in Korean Patent Publication No. 10-2022-0014454, and the compound described in JP 2023-013321 A can also be used. The content of the UV absorber in the total solids content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorber may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

[0246] <<Polymerization Inhibitor>> The curable composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Of these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the curable 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.

[0247] <<Silane Coupling Agent>> The curable composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and preferably silane compounds having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent directly bonded to a silicon atom that can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. 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 mercapto 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 curable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0248] <<Surfactant>> The curable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. 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, reference may be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0249] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of WO 2022 / 085485 can be used.

[0250] Examples of nonionic surfactants include the compounds described in paragraph 0174 of WO 2022 / 085485.

[0251] Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie). Furthermore, compounds having the following structure can also be used as the silicone surfactant.

[0252] The content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is in the above range.

[0253] <<Antioxidant>> The curable composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenolic antioxidant 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, ADK STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). Antioxidants include the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in WO 2017 / 006600, the compounds described in WO 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0254] <<Other Components>> The curable composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release promoters, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022 / 085485 can be used.

[0255] The curable composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO ２ , ZrO ２ , Al ２ O ３ , SiO ２ The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0256] The curable 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.

[0257] It is also preferable that the curable 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 curable composition is 1,000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0258] In view of environmental regulations, the curable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0259] The curable 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 curable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

[0260] From the standpoint 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 curable composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solids content of the curable composition. The curable 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 curable 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 curable 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.

[0261] The water content of the curable 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.

[0262] The curable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.), adjusting the film thickness, etc. The viscosity value can be appropriately selected 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 with the temperature adjusted to 25°C.

[0263] <<Storage Container>> The container for storing the curable composition is not particularly limited, and any known container can be used. In addition, the container described in paragraph 0187 of WO 2022 / 085485 can be used as the storage container.

[0264] <Method for preparing curable composition> The curable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the curable composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the curable 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 curable composition.

[0265] The preparation of the curable 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, for example, the process and disperser described in "Dispersion Technology Encyclopedia," published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid / Liquid Dispersion System) - Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, and paragraph 0022 of JP 2015-157893 A. In addition, in the process for dispersing pigments, particle refinement may be performed in a salt milling process. For details on the materials, equipment, processing conditions, etc. used in the salt milling process, 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 curable composition may contain 1 to 10,000 ppm of the beads.

[0266] When preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign matter, reducing defects, etc. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022 / 085485.

[0267] <Film> The film of the present invention is a film obtained from the curable composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, infrared transmission filters, and infrared cut filters.

[0268] 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.

[0269] 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.

[0270] <Pixel Manufacturing Method> A pixel manufacturing method using the curable composition of the present invention will be described. The pixel manufacturing method includes the steps of forming a curable composition layer on a support using the curable composition of the present invention, exposing the curable composition layer to light in a pattern, and developing and removing the unexposed areas of the curable composition layer. If necessary, a step of drying the curable composition layer (pre-baking step) and a step of heat-treating the developed pattern (pixel) (post-baking step) may also be provided.

[0271] In the step of forming a curable composition layer, the curable composition layer is formed on a support using the curable 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.

[0272] Known methods can be used as the coating method for the curable composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, the method described in JP 2009-145395 A); inkjet (for example, on-demand method, piezo method, thermal method), various printing methods such as nozzle jet and other ejection printing, 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 mentioned. In addition, the coating method described in paragraph 0207 of WO 2022 / 085485 A can also be used.

[0273] The curable 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.

[0274] Next, the curable composition layer is exposed to light in a pattern (exposure step). For example, the curable 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 portion to be cured.

[0275] Examples of radiation (light) that can be used for exposure include g-line and i-line. 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 line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (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.

[0276] In the exposure step, the curable 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).

[0277] 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 repeatedly irradiated and paused in a short cycle (for example, on the order of milliseconds or less).

[0278] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm ２ is preferred, 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 ~100000W / m ２ (For example, 5000 W / m ２ , 15000W / m２ , 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 20,000 W / m ２ etc.

[0279] Next, the unexposed portions of the curable composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the curable composition layer can be developed and removed using a developer. As a result, the unexposed portions of the curable 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 removability, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.

[0280] 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.

[0281] 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 achieve the above conditions for the developed film. 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.

[0282] <Optical Filter> The film of the present invention can be used in an optical filter. Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and a color filter is 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 a colored pixel.

[0283] 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 resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ２ O ３ , Mo, SiO ２ , Si ２ N ４ For example, in the case of a protective layer intended to block oxygen, the protective layer may contain a polyol resin and SiO ２ and Si ２ N ４ In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.

[0284] 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.

[0285] The protective layer may contain additives such as organic or inorganic fine particles, absorbers for 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 for light of specific wavelengths can be used. The content of these additives can be adjusted as appropriate, 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.

[0286] As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

[0287] 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.

[0288] <Solid-state imaging device> 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.

[0289] The substrate includes a plurality of photodiodes constituting a 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 (on the side 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 equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

[0290] <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."

[0291] <Photopolymerization Initiator> The photopolymerization initiator of the present invention includes a compound represented by the above formula (1A) or (1B).

[0292] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed 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.

[0293] <Synthesis Examples> (Synthesis Example 1) Synthesis Method of Compound A-1 18.5 g of 1,2,3,4-tetrahydrocarbazol-4-one was added to a mixed solution of 200 mL of pyridine and 200 mL of isopropyl alcohol and stirred at 25°C to completely dissolve. 12.5 g of hydroxylamine hydrochloride was added thereto and stirred at 25°C for 24 hours. The resulting reaction solution was crystallized from 500 mL of 2 M aqueous hydrochloric acid, and the resulting crystals were collected by filtration. These were recrystallized from 100 mL of acetonitrile to obtain 16.4 g of 1,2,3,9-tetrahydro-4H-carbazol-4-one oxime. 1,2,3,9-tetrahydro-4H-carbazol-4-one oxime was dissolved in 200 mL of ethyl acetate, 15.3 g of triethylamine was added, and the mixture was cooled and stirred at 5°C. 9.1 g of acetyl chloride was added dropwise thereto over 10 minutes, and the mixture was further stirred at 25°C for 2 hours. The resulting reaction solution was washed three times with 50 mL of pure water, and the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (hexane / ethyl acetate=10 / 1) to obtain 9.8 g of compound (A-1). １ HNMR (400MHz) δ = 1.99 (m, 2H), 2.19 (s, 3H), 2.51 (t, 2H), 2.75 (t, 2H), 7.15 (d, 2H), 7.36 (s, 1H), 8.00 (s, 1H), 12.6 (brs, 1H)

[0294] Synthesis Example 2: Method for Synthesizing Compound A-7 18.5 g of 1,2,3,4-tetrahydrocarbazol-4-one, 14.1 g of 4-fluoronitrobenzene, and 18.9 g of potassium carbonate were dissolved in 300 mL of dimethylformamide. This was heated and stirred at 150°C for 6 hours under a nitrogen atmosphere. The resulting reaction solution was poured into a mixed solution of 500 mL of methanol and 300 mL of water, and the resulting crystals were collected by filtration. In this way, 28.7 g of 9-(4-nitrophenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one was obtained. 10.1 g of Compound (A-7) was obtained in the same manner as in Synthesis Example 1, except that 9-(4-nitrophenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one was used instead of 1,2,3,4-tetrahydrocarbazol-4-one. １ HNMR (400MHz) δ = 2.02 (m, 2H), 2.21 (s, 3H), 2.58 (t, 2H), 2.78 (t, 2H), 7.4-7.6 (m, 3H), 7.68 (d, 2H), 8.38 (d, 2H), 8.48 (d, 1H)

[0295] Synthesis Example 3 Synthesis Method of Compound A-19 11.7 g of compound (A-19) was obtained in the same manner as in Synthesis Example 2, except that 4-fluorobenzophenone was used instead of 4-fluoronitrobenzene. １ HNMR (400MHz) δ = 2.03 (m, 2H), 2.14 (s, 3H), 2.63 (t, 2H), 2.72 (t, 2H), 7.3-8.0 (m, 12H), 8.28 (d, 1H)

[0296] Synthesis Example 4 Synthesis Method of Compound A-21 12.3 g of compound (A-21) was obtained in the same manner as in Synthesis Example 2, except that 4-fluorobenzophenone was used instead of 4-fluoronitrobenzene and benzoyl chloride was used instead of acetyl chloride. １ HNMR (400MHz) δ = 1.97 (m, 2H), 2.16 (s, 3H), 2.55 (t, 2H), 2.79 (t, 2H), 7.3-8.0 (m, 17H), 8.39 (d, 1H)

[0297] Synthesis Example 5 Synthesis Method of Compound A-45 7.9 g of 1-methoxynaphthalene was dissolved in 50 mL of chlorobenzene, 6.2 g of aluminum chloride was added, and the mixture was stirred at 5°C for 10 minutes. 8.1 g of 4-fluoro-2-methylbenzoyl chloride was added dropwise over 10 minutes, and the reaction solution was heated to 25°C and stirred for an additional 2 hours. The resulting reaction solution was added to 200 mL of ice water, and the organic layer was separated and concentrated. 100 mL of methanol was added to the mixture, and the precipitated crystals were collected by filtration to obtain 13.2 g of (4-fluoro-2-methylphenyl)(4-methoxynaphthalen-1-yl)methanone. 13.8 g of compound (A-45) was obtained in the same manner as in Synthesis Example 2, except that the (4-fluoro-2-methylphenyl)(4-methoxynaphthalen-1-yl)methanone obtained above was used instead of 4-fluoronitrobenzene in Synthesis Example 2. １ HNMR (400MHz) δ = 1.97 (m, 2H), 2.16 (s, 3H), 2.48 (s, 3H), 2.55 (t, 2H), 2.79 (t, 2H), 3.79 ( s, 3H), 6.78 (d, 1H), 7.3-8.0 (m, 8H), 8.07 (d, 1H), 8.39 (d, 1H), 8.48 (d, 1H), 9.12 (d, 1H)

[0298] Synthesis Example 6 Synthesis Method of Compound A-65 8.4 g of dibenzofuran was dissolved in 100 mL of chlorobenzene, 6.2 g of aluminum chloride was added, and the mixture was stirred at 5°C for 10 minutes. 8.1 g of 4-fluoro-2-methylbenzoyl chloride was added dropwise over 10 minutes, and the reaction solution was heated to 25°C and stirred for an additional 2 hours. Next, 8.5 g of aluminum chloride was added, and 10.5 g of o-toluoyl chloride was added thereto, and the reaction solution was heated to 70°C and stirred for an additional 6 hours. The resulting reaction solution was added to 300 mL of ice water cooled to 0°C, 200 mL of methanol, and 100 mL of 2N aqueous hydrochloric acid to precipitate crystals. The precipitated crystals were collected by filtration and reslurried in 200 mL of methanol for purification, yielding 16.9 g of (8-(4-fluoro-2-methylbenzoyl)dibenzo[b,d]furan-2-yl)(o-tolyl)methanone. 11.8 g of compound (A-65) was obtained in the same manner as in Synthesis example 2, except that (8-(4-fluoro-2-methylbenzoyl)dibenzo[b,d]furan-2-yl)(o-tolyl)methanone obtained above was used instead of 4-fluoronitrobenzene in Synthesis example 2. １ HNMR (400MHz) δ = 1.97 (m, 2H), 2.16 (s, 3H), 2.48 (s, 3H), 2.49 (s, 3H), 2.55 (t, 2H), 2.79 (t, 2H), 7.0-8.5 (m, 17H)

[0299] Synthesis Example 7 Synthesis Method of Compound A-67 Compound (A-67) was obtained in the same manner as in Synthesis Example 6, except that N-ethylcarbazole was used instead of dibenzofuran. １ HNMR (400MHz) δ = 1.37 (t, 3H), 1.98 (m, 2H), 2.15 (s, 3H), 2.49 (s, 3H), 2.50 (s, 3H), 2.56 (t, 2H), 2.72 (t, 2H), 4.22 (q, 2H), 7.0-8.5 (m, 15H), 8.74 (s, 1H), 8,79 (s, 1H)

[0300] Synthesis Example 8 Synthesis Method of Compound A-69 Compound (A-69) was obtained in the same manner as in Synthesis Example 6, except that 2-nitro-9,9-dipropyl-9H-fluorene was used instead of dibenzofuran. １HNMR (400MHz) δ = 0.89 (t, 6H), 1.30 (m, 4H), 1.83 (t, 4H), 2.00 (m, 2H), 2.20 (s, 3H), 2.48 (s, 3H), 2.56 (t, 2H), 2.76 (t, 2H), 7.3-8.5 (m, 13H)

[0301] Synthesis Example 9 Synthesis Method of Compound A-87 18.5 g of 1,2,3,4-tetrahydrocarbazol-4-one was added to 200 mL of tetrahydrofuran and stirred at 25°C until completely dissolved. This was cooled to 5°C, and 50 g of a 28% sodium methoxide methanol solution was added, followed by further stirring at 5°C for 1 hour. Next, 12.5 g of isoamyl nitrite was added dropwise over 30 minutes, and the temperature was raised to 25°C and further stirred for 2 hours. The resulting reaction solution was dissolved in 500 mL of ethyl acetate and washed three times with 100 mL of pure water. The organic layer was concentrated, and the resulting solid was collected by filtration. This was recrystallized from 100 mL of acetonitrile to obtain 12.1 g of 3-(hydroxyimino)-1,2,3,9-tetrahydro-4H-carbazol-4-one. 3-(hydroxyimino)-1,2,3,9-tetrahydro-4H-carbazol-4-one was dissolved in 200 mL of ethyl acetate, and 15.3 g of triethylamine was added, followed by cooling and stirring at 5°C. 9.1 g of acetyl chloride was added dropwise to the solution over 10 minutes, and the mixture was further stirred at 25°C for 2 hours. The resulting reaction solution was washed three times with 50 mL of pure water, and the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 10 / 1), yielding 8.8 g of compound (A-87). １ HNMR (400MHz) δ = 2.22 (s, 3H), 2.40 (t, 2H), 2.81 (t, 2H), 7.13 (d, 2H), 7.36 (d, 1H), 8.00 (d, 1H) 13.8 (brs, 1H)

[0302] Synthesis Example 10 Method for Synthesizing Compound A-93 7.1 g of compound (A-93) was obtained in the same manner as in Synthesis Example 9, except that 9-(4-nitrophenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one was used instead of 1,2,3,4-tetrahydrocarbazol-4-one in Synthesis Example 9. １HNMR (400MHz) δ = 2.21 (s, 3H), 2.62 (t, 2H), 2.78 (t, 2H), 7.4-7.6 (m, 3H), 7.68 (d, 2H), 8.38 (d, 2H), 8.48 (d, 1H)

[0303] Synthesis Example 11 Method for Synthesizing Compound (A-105) 11.7 g of compound (A-105) was obtained in the same manner as in the synthesis method for compound (A-93), except that 4-fluorobenzophenone was used instead of 4-fluoronitrobenzene. １ HNMR (400MHz) δ = 2.19 (s, 3H), 2.42 (t, 2H), 2.77 (t, 2H), 7.3-8.0 (m, 12H), 8.28 (d, 1H)

[0304] Synthesis Example 12 Synthesis Method of Compound A-151 16.9 g of (8-(4-fluoro-2-methylbenzoyl)dibenzo[b,d]furan-2-yl)(o-tolyl)methanone was obtained in the same manner as in Synthesis Example 6. This was dissolved in 300 mL of dimethylformamide, followed by the addition of 11.1 g of 1,2,3,4-tetrahydrocarbazol-4-one and 28.1 g of potassium carbonate. The mixture was heated and stirred at 150°C for 6 hours under a nitrogen atmosphere. The resulting reaction solution was poured into a mixed solution of 500 mL of methanol and 300 mL of water, and the resulting crystals were collected by filtration. In this way, 20.3 g of 9-(3-methyl-4-(8-(2-methylbenzoyl)dibenzo[b,d]furan-2-carbonyl)phenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one was obtained. Compound (A-151) was obtained in 13.9 yen in the same manner as in Synthesis example 9, except that 9-(3-methyl-4-(8-(2-methylbenzoyl)dibenzo[b,d]furan-2-carbonyl)phenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one obtained above was used instead of 1,2,3,4-tetrahydrocarbazol-4-one in Synthesis example 9. １ HNMR (400MHz) δ = 2.16 (s, 3H), 2.48 (s, 3H), 2.49 (s, 3H), 2.50 (t, 2H), 2.71 (t, 2H), 7.0-8.5 (m, 17H)

[0305] (Synthesis Example 13) Method for synthesizing compound A-174

[0123] 8.6 g of compound A-174 was obtained in the same manner as in Synthesis example 12, except that 4-(3-methyl-4-(7-nitro-9,9-dipropyl-9H-fluorene-2-carbonyl)phenyl)-3,4-dihydrocyclopenta[b]indol-1(2H)-one was used instead of 9-(3-methyl-4-(8-(2-methylbenzoyl)dibenzo[b,d]furan-2-carbonyl)phenyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one in Synthesis example 12. １ HNMR (400MHz) δ = 0.89 (t, 6H), 1.30 (m, 4H), 1.83 (t, 4H), 2.20 (s, 3H), 2.40 (t, 2H), 2.48 (s, 3H), 2.69 (t, 2H), 7.3-8.5 (m, 13H)

[0306] <Preparation of Curable Composition> Curable compositions were prepared by mixing the types of materials shown in the table below with 0.2 parts by mass of KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant, 0.2 parts by mass of Adekastab AO-80 (manufactured by ADEKA Corporation) as an antioxidant, and 0.01 parts by mass of p-methoxyphenol as a polymerization inhibitor. The dispersions used were prepared as follows. When two or more types of materials are listed in the "Type" column of the table, the total amount of each material, using equal amounts, is listed in the "Parts by mass" column.

[0307] (Dispersion) A mixture was obtained by mixing the materials listed in the Dispersion column in the table below. The mixture was then subjected to a dispersion treatment using an Ultra Apex Mill manufactured by Kotobuki Industries Co., Ltd. as a circulating dispersion device (bead mill) to produce a dispersion.

[0308]

[0309] Details of the materials listed in the table above are as follows:

[0310] (Colorants) PG36: C.I. Pigment Green 36 (green pigment) PG58: C.I. Pigment Green 58 (green pigment) PY129: C.I. Pigment Yellow 129 (yellow pigment) PY138: C.I. Pigment Yellow 138 (yellow pigment) PY139: C.I. Pigment Yellow 139 (yellow pigment) PY150: C.I. Pigment Yellow 150 (yellow pigment) PY185: C.I. Pigment Yellow 185 (yellow pigment) PY215: C.I. Pigment Yellow 215 (yellow pigment) PR177: C.I. Pigment Red 177 (red pigment) PR254: C.I. C.I. Pigment Red 254 (red pigment) PR264: C.I. Pigment Red 264 (red pigment) PR272: C.I. Pigment Red 272 (red pigment) PR291: C.I. Pigment Red 291 (red pigment) PB15:6: C.I. Pigment Blue 15:6 (blue pigment) PV23: C.I. Pigment Violet 23 (purple pigment) P-1: Compound having the following structure (pyrrolopyrrole compound, infrared absorbing pigment) P-2: Compound having the following structure (squarylium compound, infrared absorbing pigment) P-3: Titanium Black (TiO ｘ N ｙ ) (black pigment, manufactured by Mitsubishi Materials Corporation) P-4: Titanium oxide (white pigment, TTO-51(C), manufactured by Ishihara Sangyo Kaisha Ltd.) P-5: Compound having the following structure (magenta dye)

[0311] (Dispersing aid) Syn-1: Compound having the following structure (pigment derivative) Syn-2: Compound having the following structure (pigment derivative) Syn-3: Compound having the following structure (a / b / c=10 / 70 / 20 (mol %), weight average molecular weight: 600) Syn-4: Compound having the following structure (pigment derivative) Syn-5: a compound having the following structure Syn-6: a compound having the following structure Syn-7: a compound having the following structure

[0312] (Resin) C2-1: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000, acid value: 67 mgKOH / g) C2-2: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 23,000, acid value: 59 mg KOH / g) C2-3: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 18,000, acid value: 69 mg KOH / g) C2-4: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 23,000, acid value: 67 mg KOH / g) C2-5: Resin having the following structure (weight average molecular weight 10,000, acid value 85 mgKOH / g) C2-6: Resin having the following structure (weight average molecular weight 18,000, acid value 82 mgKOH / g) C2-7: Resin having the following structure (weight average molecular weight 8000, acid value 50 mgKOH / g)

[0313] B-1: Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight: 11,000; acid value: 69 mg KOH / g) B-2: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight-average molecular weight: 21,000) B-3: Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight: 12,000; acid value: 80 mg KOH / g)

[0314] (Polymerizable Compound) M-1: A mixture of compounds having the following structure (a mixture of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) in a molar ratio of 7:3) M-2: Compound of the following structure M-3: Compound having the following structure M-4: Compound having the following structure M-5: Compound having the following structure

[0315] (Photopolymerization initiators) A-1 to A-174: Compounds A-1 to A-174 shown as specific examples of the specific compounds described above. cA-1, cA-2: Compounds having the following structure (comparative compounds). I-1 to I-15: Compounds having the following structure (other photopolymerization initiators).

[0316] (Additives) T-1 to T-8: Compounds having the following structures

[0317] (Solvent) S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclopentanone S-4: 3-methoxybutanol S-5: Cyclohexanone S-6: 3-methoxypropanol

[0318] <Evaluation> (Evaluation of Thermal Stability) An undercoat agent (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 μm, and the wafer was heated on a hot plate at 220° C. for 300 seconds to form an undercoat layer, thereby obtaining a silicon wafer with an undercoat layer. Each of the curable compositions obtained above in Examples 1 to 7, 24 to 33, 50 to 60, 75 to 85, 100, 116 to 130, 132 to 139, 141 to 145, 161 to 164, 179 to 184, and Comparative Examples 1 to 3 was applied by spin coating onto the undercoat layer of the undercoat layer-equipped silicon wafer so that the film thickness after application would be 0.6 μm, and the wafer was then heated on a hot plate at 100° C. for 2 minutes (heating condition 1) or at 150° C. for 2 minutes (heating condition 2) to form a composition layer. The composition layer formed under heating condition 1 is referred to as composition layer (X), and the composition layer formed under heating condition 2 is referred to as composition layer (Y). The obtained composition layer (X) and composition layer (Y) were each eluted with tetrahydrofuran, and the area values ​​of the photopolymerization initiators contained in the composition layer (X) and composition layer (Y) were calculated using high-performance liquid chromatography. Hereinafter, the area value of the photopolymerization initiator contained in the composition layer (X) is referred to as area value (X), and the area value of the photopolymerization initiator contained in the composition layer (Y) is referred to as area value (Y). Because the composition layer (Y) was formed under higher heating conditions than the composition layer (X), the photopolymerization initiator in the composition layer (Y) is more easily decomposed than in the composition layer (X). Therefore, the area value of the photopolymerization initiator is area value (Y) ≦ area value (X). The closer the area value (Y) / area value (X) is to 1, the less the photopolymerization initiator decomposes upon heating, indicating superior thermal stability. The thermal stability performance was not evaluated for Examples 8 to 23, 34 to 49, 61 to 74, 86 to 99, 101 to 115, 131, 140, 146 to 160, and 165 to 178, in which other photopolymerization initiators were used in combination, and is indicated by "-".A: Area value (Y) / area value (X) = 1.00 B: 0.95≦area value (Y) / area value (X)<1.00 C: 0.90≦area value (Y) / area value (X)<0.95 D: 0.70≦area value (Y) / area value (X)<0.90 E: Area value (Y) / area value (X)<0.70

[0319] (Evaluation of Resolution) Each of the curable compositions obtained above in Examples 1 to 184 and Comparative Examples 1 to 3 was applied by spin coating onto the undercoat layer of the undercoat layer-attached silicon wafer so that the film thickness after application would be 0.6 μm, and then heated at 140° C. for 2 minutes using a hot plate to form a composition layer. Next, using a KrF scanner exposure machine, the obtained composition layer was irradiated with light (KrF rays) at a wavelength of 248 nm at an illuminance of 35,000 W / m through a mask having square patterns of 0.8 μm, 0.5 μm, 0.45 μm, 0.4 μm, and 0.35 μm. ２ , pulse width 20 nanoseconds, frequency 50 kHz, exposure dose 30 mJ / 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 a developer. After that, water droplets adhering to the pattern surface were removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels). The silicon wafer on which the pixels were formed was observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The minimum mask pattern at which the pattern was resolved was calculated. A: Resolved up to 0.35 μm B: Resolved up to 0.40 μm but not resolved at 0.35 μm C: Resolved up to 0.45 μm but not resolved at 0.40 μm or less D: Resolved up to 0.50 μm but not resolved at 0.45 μm or less E: Resolved up to 0.80 μm but not resolved at 0.50 μm or less

[0320] (Sensitivity Evaluation) Each of the curable compositions obtained above in Examples 1 to 184 and Comparative Examples 1 to 3 was applied by spin coating onto the undercoat layer of the undercoat layer-attached silicon wafer so that the film thickness after application would be 0.6 μm, and then heated at 140° C. for 2 minutes using a hot plate to form a composition layer. Next, using a KrF scanner exposure machine, the obtained composition layer was irradiated with light (KrF rays) with a wavelength of 248 nm through a mask having a 0.5 μm square pattern at an illuminance of 35,000 W / m ２ , pulse width 20 nanoseconds, frequency 50 kHz, exposure dose 20 mJ / cm ２ ~300 mJ / cm ２ The exposure was carried out by changing the irradiation amount within the range. Next, the composition layer after exposure was subjected to shower development at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. Thereafter, water droplets adhering to the pattern surface were removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels). The silicon wafer on which pixels had been formed was observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The exposure amount required for the pattern line width to reach 0.6 μm in the observed pixels was calculated, and the sensitivity was evaluated according to the following evaluation criteria. A: Exposure amount of 50 mJ / cm ２ B: The exposure amount is 50 mJ / cm or less ２ exceeding 70 mJ / cm ２ C: The exposure amount is 70 mJ / cm or less ２ exceeding 100 mJ / cm ２ D: The exposure amount is 100 mJ / cm or less ２ exceeding 150 mJ / cm ２ E: The exposure amount is 150 mJ / cm or less ２ exceed

[0321] (Evaluation of Adhesion) Each of the curable compositions obtained above in Examples 1 to 184 and Comparative Examples 1 to 3 was applied by spin coating onto the undercoat layer of the undercoat layer-attached silicon wafer so that the film thickness after application would be 0.6 μm, and then heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, using a KrF scanner exposure machine, the obtained composition layer was irradiated with light (KrF line) with a wavelength of 248 nm through a mask engraved with a 0.6 μm checkered pattern at an illuminance of 35,000 W / m ２ , pulse width 20 nanoseconds, frequency 50 kHz, exposure dose 30 mJ / 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 puddle development at 23°C for 60 seconds. The layer was then rinsed with pure water for 20 seconds using a spin shower, and then washed with pure water. Water droplets adhering to the pattern surface were then removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels). The silicon wafer with the formed pixels was observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The ratio of missing pixels among 100 pixels was observed from the scanning electron microscope photograph to evaluate adhesion. The evaluation criteria are as follows: A: The ratio of missing pixels is 0%. B: The ratio of missing pixels is greater than 0% and less than 10%. C: The ratio of missing pixels is greater than 10% and less than 20%. D: The ratio of missing pixels is greater than 20% and less than 50%. E: The ratio of missing pixels is greater than 50%.

[0322]

[0323] As shown in the above table, the examples were superior to the comparative examples in the evaluations of thermal stability, resolution, sensitivity and adhesion.

[0324] 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 curable composition comprising a photopolymerization initiator, a polymerizable compound, and a solvent, wherein the photopolymerization initiator comprises a compound A represented by formula (1A) or formula (1B); In formula (1A) and formula (1B), R １ａ and R １ｂ each independently represents a hydrogen atom or a monovalent organic group; R ２ａ and R ２ｂ each independently represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; １ａ and X １ｂ are each independently O, S, or NR Ｘ１ or CR Ｘ２ R Ｘ３ represents R Ｘ１ ~R Ｘ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R Ｘ２ and R Ｘ３ may be bonded via a single bond or a divalent linking group to form a ring, R Ｘ１ ~R Ｘ３ Either of the above and L １ａ , L １ｂ , R １ａ Or R ７ｂ may be bonded via a single bond or a divalent linking group to form a ring, L １ａ and L １ｂ each independently represents a single bond or a divalent linking group; R ５ａ ~R ８ａ and R ５ｂ ~R ８ｂ each independently represents a hydrogen atom or a substituent; R ５ａ ~R ８ａ adjacent two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ａ and R ５ａ may be bonded via a single bond or a divalent linking group to form a ring, R ５ｂ ~R ７ｂ adjacent two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ｂ and R ５ｂ may be bonded via a single bond or a divalent linking group to form a ring, R １ｂ and R ８ｂ may be bonded via a single bond or a divalent linking group to form a ring, and n represents 0 or 1.

2. L in the formula (1A) １ａ and L of formula (1B) １ｂ The curable composition of claim 1 , wherein each is independently a single bond or an alkylene group.

3. R ​​in the above formula (1A) １ａ and R of formula (1B) １ｂ each independently represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and the substituent is an alkyl group, an aryl group, a heteroaryl group, -OR ２０１ , -SR ２０１ , -COR ２０１ , -SO ２ R ２０１ , -NR ２０２ R ２０３ , -CONR ２０２ R ２０３ , -NR ２０４ C.O.R. ２０５ , -OCOR ２０１ , -COOR ２０１ , -SCOR ２０１ , -OCSR ２０１ , -COSR ２０１ , -CSOR ２０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ２０１ ~R ２０５ The curable composition according to claim 1 or 2, wherein each independently represents a monovalent organic group.

4. R in the above formula (1A) １ａ and R of formula (1B) １ｂ are each independently a substituted aryl group or a substituted heteroaryl group, the substituent of the aryl group or the heteroaryl group being -COR ２０１ or -SO ２ R ２０１ And R ２０１ represents an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, and the substituent which the aromatic ring group or the heterocyclic group may have is an alkyl group, an aryl group, a heteroaryl group, -OR ３０１ , -SR ３０１ , -COR ３０１ , -SO ２ R ３０１ , -NR ３０２ R ３０３ , -CONR ３０２ R ３０３ , -NR ３０４ C.O.R. ３０５ , -OCOR ３０１ , -COOR ３０１ , -SCOR ３０１ , -OCSR ３０１ , -COSR ３０１ , -CSOR ３０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ３０１ ~R ３０５ The curable composition according to claim 3 , wherein each independently represents a monovalent organic group.

5. The curable composition according to claim 1 or 2, wherein the compound A is a compound represented by formula (4). In formula (4), R ４２ represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; L ４ represents a single bond or an alkylene group having 1 to 4 carbon atoms; R ４５ ~R ４８ each independently represents a hydrogen atom or a substituent; R ４５ ~R ４８ adjacent two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ４９ represents an alkyl group, an aryl group, or a halogen atom, and when k is 2 or more, a plurality of R ４９ may be the same or different, and multiple R ４９ Two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; ５０ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -OR ５０１ , -SR ５０１ , -COR ５０１ , -SO ２ R ５０１ , -NR ５０２ R ５０３ , -CONR ５０２ R ５０３ , -NR ５０４ C.O.R. ５０５ , -OCOR ５０１ , -COOR ５０１ , -SCOR ５０１ , -OCSR ５０１ , -COSR ５０１ , -CSOR ５０１ , a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or a halogen atom; R ５０１ ~R ５０５ each independently represents a monovalent organic group; R ５１ and R ５２ each independently represents a hydrogen atom or an alkyl group; R ５１ and R ５２ may be bonded via a single bond or a divalent linking group to form a ring, R ４９ is R ４５ Or R ５１ may be bonded to R via a single bond or a divalent linking group to form a ring; ４９ and R ５０ may be bonded via a single bond or a divalent linking group to form a ring, R ５２ and L ４ may be bonded via a single bond or a divalent linking group to form a ring; k represents an integer of 0 to 4.

6. The curable composition according to claim 1 or 2, wherein the photopolymerization initiator further comprises a photopolymerization initiator other than compound A.

7. The curable composition according to claim 1 or 2, further comprising a coloring material.

8. The curable composition according to claim 1 or 2, further comprising an amine compound.

9. The curable composition according to claim 1 or 2, further comprising a chain transfer agent.

10. The curable composition according to claim 1 or 2, further comprising a resin.

11. The hardenable composition of claim 10, wherein the resin comprises a resin having crosslinkable groups.

12. A method for manufacturing a pixel, comprising the steps of: forming a curable composition layer on a support using the curable composition according to claim 1 or 2; exposing the curable composition layer in a pattern by irradiating it with light having a wavelength of 150 to 300 nm; and developing and removing the unexposed areas of the curable composition layer.

13. A film obtained by curing the curable composition according to claim 1 or 2.

14. A solid-state imaging device comprising the film according to claim 13.

15. An image display device comprising the film according to claim 13.

16. A photopolymerization initiator comprising a compound represented by formula (1A) or formula (1B); In formula (1A) and formula (1B), R １ａ and R １ｂ each independently represents a hydrogen atom or a monovalent organic group; R ２ａ and R ２ｂ each independently represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; １ａ and X １ｂ are each independently O, S, or NR Ｘ１ or CR Ｘ２ R Ｘ３ represents R Ｘ１ ~R Ｘ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R Ｘ２ and R Ｘ３ may be bonded via a single bond or a divalent linking group to form a ring, R Ｘ１ ~R Ｘ３ Either of the above and L １ａ , L １ｂ , R １ａ Or R ７ｂ may be bonded via a single bond or a divalent linking group to form a ring, L １ａ and L １ｂ each independently represents a single bond or a divalent linking group; R ５ａ ~R ８ａ and R ５ｂ ~R ８ｂ each independently represents a hydrogen atom or a substituent; R ５ａ ~R ８ａ adjacent two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ａ and R ５ａ may be bonded via a single bond or a divalent linking group to form a ring, R ５ｂ ~R ７ｂ adjacent two of R may be bonded to each other via a single bond or a divalent linking group to form a ring; １ｂ and R ５ｂ may be bonded via a single bond or a divalent linking group to form a ring, R １ｂ and R ８ｂ may be bonded via a single bond or a divalent linking group to form a ring, and n represents 0 or 1.

Images