WO2025154520A1 - Photocurable composition, film, optical filter, solid-state imaging element, and image display device - Google Patents

Abstract

Provided is a photocurable composition containing: at least one compound A selected from compounds represented by any of formulae (A-1) to (A-6); a resin; and a photopolymerisation initiator, the content of compound A in the total solid content of the photocurable composition being 0.005 to 2 mass%. Further provided are: a film obtained using the aforementioned photocurable composition; an optical filter; a solid-state imaging element; and an image display device.

Description

Photocurable composition, film, optical filter, solid-state imaging device and image display device

The present invention relates to a photocurable composition. The present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device that use the photocurable composition.

　Camcorders, digital still cameras, mobile phones with cameras, and the like use solid-state imaging elements such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors). Solid-state imaging elements are also equipped with optical filters such as color filters. Optical filters are manufactured using, for example, a photocurable composition that contains a polymerizable compound and a photopolymerization initiator (see Patent Document 1).

JP 2020-181041 A

In recent years, progress has been made in miniaturizing the pattern size of optical filters used in solid-state imaging devices. However, as the pattern size becomes finer, there is a tendency for adhesion to the support to become insufficient.

In addition, there is a demand for further improvement in the solvent resistance of films obtained using photocurable compositions.

The inventors have studied the composition described in Patent Document 1 and found that there is room for further improvement in the solvent resistance of the resulting film and its adhesion to the support.

Therefore, an object of the present invention is to provide a photocurable composition capable of forming a film having excellent adhesion and solvent resistance. In addition, the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.

The inventors have found through their research that the above object can be achieved by using the photocurable composition described below, and have completed the present invention. Therefore, the present invention provides the following.

<1> A photocurable composition comprising at least one compound A selected from the compounds represented by any one of formulas (A-1) to (A-6), a resin, and a photopolymerization initiator,
a photocurable composition, the content of the compound A being 0.005 to 2 mass% based on the total solid content of the photocurable composition;
In the formula, R ^a1 to R ^a13 each independently represent a hydrogen atom or a methyl group.
<2> The photocurable composition according to <1>, wherein the compound A is at least one selected from the group consisting of a compound represented by formula (A1-01), a compound represented by formula (A1-02), a compound represented by formula (A5-01), and a compound represented by formula (A5-02).
<3> The photocurable composition according to <1> or <2>, further comprising a tri- to hexa-functional polymerizable compound having 3 to 6 ethylenically unsaturated bond-containing groups, the tri- to hexa-functional polymerizable compound having a structure different from that of the compound A.
<4> The photocurable composition according to any one of <1> to <3>, wherein the resin includes a resin having an ethylenically unsaturated bond-containing group.
<5> The photocurable composition according to <4>, in which the resin having an ethylenically unsaturated bond-containing group contains a group represented by any one of formulas (b-1) to (b-3).
In formula (b-1), * represents a bond, R ^b1 represents a hydrogen atom or a methyl group, and R ^b2 represents a hydrogen atom or an organic group;
In formula (b-2), * represents a bond, and R ^b3 represents a hydrogen atom or a methyl group;
In formula (b-3), * represents a bond, R ^b4 represents a hydrogen atom or a methyl group, and R ^b5 represents a hydrogen atom or an organic group.
<6> The photocurable composition according to any one of <1> to <5>, further comprising a colorant.
<7> The photocurable composition according to any one of <1> to <6>, further comprising a compound having a quaternary ammonium cation.
<8> A film obtained by using the photocurable composition according to any one of <1> to <7>.
<9> An optical filter having the film according to <8>.
<10> A solid-state imaging device having the film according to <8>.
<11> An image display device having the film according to <8>.

The present invention provides a photocurable composition capable of forming a film having excellent adhesion and solvent resistance. The present invention also provides a film, an optical filter, a solid-state imaging device, and an image display device.

The present invention will be described in detail below.
In this specification, the use of "to" means that the numerical values before and after it are included as the lower limit and upper limit.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "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 represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
In this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl.
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the weight average molecular weight and number average molecular weight are values calculated as polystyrene standards measured by GPC (gel permeation chromatography).
In this specification, the total solids content refers to the total mass of all components of the composition excluding the solvent.
In this specification, a pigment means a coloring material that is difficult to dissolve in a solvent.
In this specification, the term "process" 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.

<Photocurable composition>
The photocurable composition of the present invention comprises
A photocurable composition comprising at least one compound A selected from the compounds represented by any one of formulas (A-1) to (A-6), a resin, and a photopolymerization initiator,
The photocurable composition is characterized in that the content of the compound A in the total solid content of the photocurable composition is 0.005 to 2 mass %.

By using the photocurable composition of the present invention, a film having excellent adhesion and solvent resistance can be formed. The reason for such effects is presumed to be as follows.
The compound A contains two or three (meth)acryloyl groups in one molecule, and further contains an OH group or an NH group, so that it is presumed that the OH group or NH group of these compounds acts as a chain transfer agent while being a radical polymerizable compound. Therefore, it is presumed that the radical polymerizability of the photocurable composition during exposure can be further improved. In addition, it is presumed that the OH group or NH group of the compound A also acts as a hydrogen bond donor, which can form a pseudo crosslink in the film. And, it is presumed that the content of the compound A in the total solid content of the photocurable composition is 0.005 to 2 mass%, so that the above-mentioned effects work in a well-balanced manner. Therefore, it is presumed that the film can be firmly cured to the bottom by exposure, and the solvent resistance of the obtained film and the adhesion to the support can be improved.

In addition, when the photocurable composition of the present invention is used to form a pattern by photolithography to form pixels, pixels with excellent rectangularity can be formed. For this reason, the photocurable composition of the present invention can be preferably used for forming a pattern by photolithography.

The photocurable composition of the present invention is preferably used as a photocurable composition for optical filters. Examples of optical filters include color filters, infrared transmission filters, and infrared cut filters, with color filters being preferred.

In addition, when a photocurable composition containing a coloring material is used, the amount of materials other than the coloring material decreases relatively as the content of the coloring material in the total solid content of the photocurable composition increases, so that the adhesion and solvent resistance of the resulting film to the support tend to be low for photocurable compositions with a high coloring material concentration. Furthermore, the rectangularity of the resulting pixels also tends to decrease. However, the photocurable composition of the present invention can form a film with excellent adhesion and solvent resistance even when the content of the coloring material in the total solid content of the photocurable composition is increased. Furthermore, it can also form pixels with excellent rectangularity. Therefore, the photocurable composition of the present invention exerts a particularly remarkable effect when applied to a photocurable composition with a high coloring material concentration (for example, a photocurable composition in which the content of the coloring material in the total solid content of the photocurable composition is 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more).

An example of a color filter is a filter having colored pixels that transmit light of a specific wavelength. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of a color filter can be formed using a photocurable composition that contains a chromatic colorant.

The maximum absorption wavelength of the infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the infrared cut filter in 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 maximum absorption wavelength of the infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a photocurable composition containing an infrared absorbing colorant.

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

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

The components used in the photocurable composition of the present invention are described below.

<<Specific compound (compound A)>>
The photocurable composition of the present invention contains at least one compound A selected from the compounds represented by any one of formulas (A-1) to (A-6). Hereinafter, the compound represented by any one of formulas (A-1) to (A-6) is also referred to as a specific compound.

In the formula, R ^a1 to R ^a13 each independently represent a hydrogen atom or a methyl group.

Specific examples of the specific compound include the compounds shown below.

The specific compound is preferably at least one selected from the group consisting of compounds represented by formula (A1-01), compounds represented by formula (A1-02), compounds represented by formula (A5-01), and compounds represented by formula (A5-02). According to this embodiment, the adhesion and solvent resistance of the resulting film can be further improved.

The content of the specific compound in the total solid content of the photocurable composition is 0.005 to 2 mass%. The upper limit is preferably 1.5 mass% or less, and more preferably 1 mass% or less. The lower limit is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more.

The photocurable composition of the present invention may contain only one type of specific compound, or may contain two or more types. When two or more types of specific compounds are contained, the total amount thereof falls within the above range.

<<Other polymerizable compounds>>
The photocurable composition of the present invention preferably further contains a tri- to hexa-functional polymerizable compound having 3 to 6 ethylenically unsaturated bond-containing groups (hereinafter also referred to as other polymerizable compound) which is a compound having a structure different from the above-mentioned specific compound. Examples of the ethylenically unsaturated bond-containing group contained in the other polymerizable compound include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The other polymerizable compound is preferably a radical polymerizable compound.

The other polymerizable compound is preferably a monomer. The molecular weight of the other 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.

The ethylenically unsaturated bond-containing group value (hereinafter referred to as C=C value) of the other polymerizable compound is preferably 2 to 14 mmol/g from the viewpoint of storage stability of the photocurable 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.

Specific examples of other polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of WO 2022/065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

Other preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (e.g., SR454, SR499, commercially available from Sartomer Corporation). Other polymerizable compounds include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK O Rigo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 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., Ami Aronix M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable compounds having an acidic group), Etercure 6361-100 (manufactured by Eternal Materials, polymerizable compounds having a hyperbranched structure), EBECRYL80 (tetrafunctional monomer containing amine, manufactured by Daicel-Olknes Co., Ltd.), EBECRYL7100 (bifunctional monomer containing amine, manufactured by Daicel-Olknes Co., Ltd.), CN371NS ( Bifunctional monomers containing amines, 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 hyperbranch structure described in JP-A-2023-043479, and polymerizable compounds described in JP-T-2023-529984 can also be used.

The content of other polymerizable compounds in the total solid content of the photocurable composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.

The photocurable composition preferably contains 0.05 to 20 parts by mass of the specific compound described above per 100 parts by mass of other polymerizable compounds. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. The lower limit is preferably 0.2 parts by mass or more, and more preferably 0.5 parts by mass or more.

The photocurable composition of the present invention may contain only one type of other polymerizable compound, or may contain two or more types. When two or more types of polymerizable compounds are contained, it is preferable that the total amount thereof is within the above range.

<<Resin>>
The photocurable composition of the present invention contains a resin. The resin is blended, for example, for dispersing pigments in the photocurable composition or for use as a binder. Note that a resin used mainly for dispersing pigments in the photocurable composition is also called a dispersant. However, such uses of the resin are merely examples, and the resin can also be used for purposes other than these uses.

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

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, as the resin, a resin described in paragraphs 0091 to 0099 of WO 2022/065215, a blocked polyisocyanate resin described in JP 2016-222891 A, a resin described in JP 2020-122052 A, a resin described in JP 2020-111656 A, a resin described in JP 2020-139021 A, a resin having a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP 2017-138503 A, a resin described in paragraphs 0199 to 0233 of JP 2020-186373 A, an alkali metal compound described in JP 2020-186325 A Soluble resins, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, copolymers containing epoxy groups and acid groups described in International Publication No. 2022/030445, resins described in JP 2018-135514 A, copolymers described in JP 2020-041046 A, resins described in JP 2023-033156 A, resins described in JP 2023-030386 A, resins described in JP 2023-027753 A, resins described in JP 2020-139021 A, resins described in JP 2023-074038 A, and resins described in JP 2023-079666 A can also be used.

(Specific resin)
The photocurable composition of the present invention preferably contains a resin having an ethylenically unsaturated bond-containing group (hereinafter also referred to as a specific resin).

Examples of ethylenically unsaturated bond-containing groups contained in specific resins include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

The weight average molecular weight of the specific resin is preferably 2,000 to 50,000. The upper limit is preferably 40,000 or less, and more preferably 30,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

The ethylenically unsaturated bond-containing group value (hereinafter referred to as C=C value) of the specific resin is preferably 0.1 to 2.5 mmol/g. The upper limit is preferably 2.0 mmol/g or less, more preferably 1.8 mmol/g or less. The lower limit is preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more. The C=C value of the specific resin is a numerical value representing the molar amount of the ethylenically unsaturated bond-containing group value per 1 g of solid content of the specific resin. When it can be calculated from the structural formula of the specific resin, the value calculated from the structural formula is used. In addition, when it cannot be calculated from the structural formula and can be calculated from the raw materials used in the synthesis of the specific resin, the value calculated from the raw materials used in the preparation is used. In addition, when the ethylenically unsaturated bond-containing group value of the specific resin cannot be calculated from the raw materials used in the synthesis of the specific resin, the value measured using the hydrolysis method is used. Specifically, the component (a) at the ethylenically unsaturated bond-containing group site is extracted from the specific resin by alkali treatment, and its content is measured by high performance liquid chromatography (HPLC), and calculated from the following formula: When the component (a) cannot be extracted from the specific resin by alkali treatment, a value measured by NMR (nuclear magnetic resonance) is used.
Ethylenically unsaturated bond-containing group value of specific resin [mmol/g]=(content of component (a) [ppm]/molecular weight of component (a) [g/mol])/(weight of specific resin [g]×(solid content concentration of specific resin [mass%]/100)×10)

The specific resin preferably contains a group represented by any one of formulas (b-1) to (b-3), and more preferably contains a group represented by formula (b-1) or (b-3). According to this embodiment, a film having excellent adhesion to the support and solvent resistance can be formed.
In formula (b-1), * represents a bond, R ^b1 represents a hydrogen atom or a methyl group, and R ^b2 represents a hydrogen atom or an organic group;
In formula (b-2), * represents a bond, and R ^b3 represents a hydrogen atom or a methyl group;
In formula (b-3), * represents a bond, R ^b4 represents a hydrogen atom or a methyl group, and R ^b5 represents a hydrogen atom or an organic group.

The organic group represented by R ^b2 in formula (b-1) and R ^b5 in formula (b-3) includes an alkyl group, an aryl group, and a heteroaryl group.
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. The alkyl group may have a substituent. Examples of the substituent include an alkoxy group, an aryloxy group, -NR ^A111 R ^A112 , -SO ₂ NR ^A113 R ^A114 , -COOR ^A115 , and -CONR ^A116 R ^A117 . R ^A111 to R ^A117 each independently represent an alkyl group or an aryl group.
The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxy group, an aryloxy group, -NR ^A111 R ^A112 , -SO ₂ NR ^A113 R ^A114 , -COOR ^A115 , -CONR ^A116 R ^A117 , and the like. R ^A111 to R ^A117 each independently represent an alkyl group or an aryl group.
The heteroaryl group is preferably a 5- or 6-membered heteroaryl group. The heteroatoms in the heteroaryl group are preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxy group, an aryloxy group, -NR ^A111 R ^A112 , -SO ₂ NR ^A113 R ^A114 , -COOR ^A115 , and -CONR ^A116 R ^A117 . R ^A111 to R ^A117 each independently represent an alkyl group or an aryl group.

R ^b2 in formula (b-1) and R ^b5 in formula (b-3) are preferably a hydrogen atom.

The specific resin is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain. The repeating unit having an ethylenically unsaturated bond-containing group in a side chain is preferably a repeating unit represented by formula (B1-1).

In the formula, Y ^b11 represents a trivalent linking group, L ^b11 represents a single bond or a divalent linking group, and A ^b11 represents an ethylenically unsaturated bond-containing group.

Examples of the trivalent linking group represented by Y ^b11 include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group. A poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferable, and a poly(meth)acrylic linking group is more preferable.

Examples of the divalent linking group represented by L ^b11 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups.

A ^b11 represents an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include
Examples of the group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a group represented by any one of the above formulas (b-1) to (b-3). A group represented by any one of the above formulas (b-1) to (b-3) is preferable, and it is more preferable to include a group represented by formula (b-1) or a group represented by formula (b-3).

The content of the repeating unit represented by formula (B1-1) is preferably 1 mol% or more, and more preferably 1 to 80 mol% of all repeating units of the specific resin. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

The specific resin may contain a repeating unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, and a phosphate group.

When the specific resin contains repeating units having an acid group, the content of the repeating units having an acid group is preferably 1 to 80 mol %, more preferably 5 to 80 mol %, and even more preferably 10 to 80 mol %, of the total repeating units of the specific resin.

When the specific resin contains a repeating unit having an acid group, the acid value of the specific resin is preferably 5 to 200 mgKOH/g. The upper limit is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 80 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and even more preferably 20 mgKOH/g or more.

The specific resin may contain a repeating unit having a graft chain. In this specification, a graft chain means a polymer chain that branches off and extends from the main chain of a repeating unit. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.

The graft chain preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic structure, polystyrene structure, polyurethane structure, polyurea structure, and polyamide structure, more preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic structure, and polystyrene structure, even more preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, and poly(meth)acrylic structure, still more preferably contains repeating units of polyester structure or polyether structure, and particularly preferably contains repeating units of polyester structure.

Examples of the repeating unit of the polyester structure include a repeating unit of a structure represented by the following formula (G-1), formula (G-4) or formula (G-5). Examples of the repeating unit of the polyether structure include a repeating unit of a structure represented by the following formula (G-2). Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of a structure represented by the following formula (G-3). Examples of the repeating unit of the polystyrene structure include a repeating unit of a structure represented by the following formula (G-6).

In the above formula, R ^G1 and R ^G2 each independently represent an alkylene group.
The number of carbon atoms in the alkylene group represented by R ^G1 is preferably 1 to 20, more preferably 2 to 16, and further preferably 2 to 12. The alkylene group is preferably linear or branched, and more preferably linear.
The number of carbon atoms in the alkylene group represented by R ^G2 is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and still more preferably 2 or 3. The alkylene group is preferably linear or branched, and more preferably linear.

In the above formula, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents --O-- or --NH--, L ^G1 represents a single bond or a divalent linking group, and R ^G4 represents a hydrogen atom or a substituent.
Examples of the divalent linking group represented by L ^G1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups combining two or more of these.
Examples of the substituent represented by R ^G4 include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.

R ^G5 represents a hydrogen atom or a methyl group, and R ^G6 represents an aryl group. The number of carbon atoms in the aryl group represented by R ^G6 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group represented by ^{R G6} may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group. Among these, groups having a steric repulsion effect are preferred, and alkyl or alkoxy groups having 5 to 24 carbon atoms are preferred. The alkyl and alkoxy groups may be linear, branched, or cyclic, and linear or branched groups are preferred.

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

In the above formula, R ^G1 and R ^G2 each represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or a divalent linking group, R ^G4 represents a hydrogen atom or a substituent, R ^G5 represents a hydrogen atom or a methyl group, R ^G6 represents an aryl group, W ¹⁰⁰ represents a hydrogen atom or a substituent, and n1 to n6 each independently represent an integer of 2 or more. R ^G1 to R ^G6 , Q ^G1 , and L ^G1 are synonymous with R ^G1 to R ^G6 , Q ^G1 , and L ^G1 described in formulas (G-1) to (G-6), and the preferred ranges are also the same.

In formulae (G-1a) to (G-6a), W ¹⁰⁰ is preferably a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group. Among these, a group having a steric repulsion effect is preferred, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

In formulas (G-1a) to (G-6a), n1 to n6 are each preferably an integer from 2 to 100, more preferably an integer from 2 to 80, and even more preferably an integer from 8 to 60.

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

The weight average molecular weight of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500. In this specification, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used in the polymerization of the repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, a macromonomer means a polymeric compound in which a polymerizable group is introduced at the polymer end. When a repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

When the specific resin contains a repeating unit having a graft chain, the content of the repeating unit having a graft chain is preferably 1 to 60 mol% of the total repeating units of the specific resin. The upper limit is preferably 50 mol% or less, and more preferably 40 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

It is also preferable that the specific resin contains a repeating unit derived from a monomer component including a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), the description in JP2010-168539A can be referred to, the contents of which are incorporated herein by reference.

Specific examples of ether dimers can be found in, for example, paragraph 0317 of JP 2013-029760 A, the contents of which are incorporated herein by reference.

It is also preferable that the specific resin contains a repeating unit derived from a compound represented by the following formula (X).
In formula (X), _R1 represents a hydrogen atom or a methyl group, _R2 represents an alkylene group having 2 to 10 carbon atoms, _R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n represents an integer of 1 to 15.

The specific resin is also preferably a resin containing a repeating unit represented by formula (Ac-2).
In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxy group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a polymer chain containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.

Examples of the group containing an aromatic carboxy group represented by Ar ¹⁰ in formula (Ac-2) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, etc. Examples of the aromatic tricarboxylic acid anhydride and aromatic tetracarboxylic acid anhydride include compounds having the following structures.

In the above formula, Q ¹ represents a single bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C(CF ₃ ) ₂ —, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

The group containing an aromatic carboxy group represented by Ar ¹⁰ may have an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxy group represented by Ar ¹⁰ include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13).

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, and are preferably an integer of 0 to 2, more preferably 1 or 2, and further preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater.
In formula (Ar-13), Q ¹ represents a single bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C(CF ₃ ) ₂ —, a group represented by formula (Q-1) above or a group represented by formula (Q-2) above.
In formulae (Ar-11) to (Ar-13), *1 represents the bonding position to ^L10 .

In formula (Ac-2), L ¹¹ represents —COO— or —CONH—, and is preferably —COO—.

The trivalent linking group represented by L ¹² in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a group combining two or more of these. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position to L ¹¹ in formula (Ac-2), and *2 represents the bonding position to P ¹⁰ in formula (Ac-2). Examples of the trivalent linking group represented by L ^12b include a hydrocarbon group; and a group in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and the like. A hydrocarbon group or a group in which a hydrocarbon group is combined with -O- is preferred.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position to L ¹¹ in formula (Ac-2), and *2 represents the bonding position to P ¹⁰ in formula (Ac-2). Examples of the trivalent linking group represented by L ^12c include a hydrocarbon group; a group in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and the like, and a hydrocarbon group is preferable.

^P10 in formula (Ac-2) represents a polymer chain containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
The polymer chain represented by ^P10 is preferably a polymer chain containing a repeating unit having a group represented by any one of the above formulas (b-1) to (b-3) at its side chain, and more preferably a polymer chain containing a repeating unit having a group represented by formula (b-1) or a group represented by formula (b-3) at its side chain.

The polymer chain represented by P ¹⁰ includes a polymer chain containing a repeating unit of at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure. The repeating unit of the polyester structure includes a repeating unit of the structure represented by the above formula (G-1), formula (G-4), or formula (G-5). The repeating unit of the polyether structure includes a repeating unit of the structure represented by the above formula (G-2). The repeating unit of the poly(meth)acrylic structure includes a repeating unit of the structure represented by the above formula (G-3). The repeating unit of the polystyrene structure includes a repeating unit of the structure represented by the above formula (G-6).

Examples of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain of the polymer chain represented by ^P10 include the repeating unit represented by the above formula (B1-1). The proportion of the repeating units having an ethylenically unsaturated bond-containing group in a side chain in all repeating units constituting ^P10 is preferably 1 mol% or more, more preferably 1 to 80 mol%. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.

The polymer chain represented by P ¹⁰ also preferably has a repeating unit containing an acid group. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group. When the polymer chain represented by P ¹⁰ contains a repeating unit having an acid group, the proportion of the repeating unit having an acid group in all repeating units constituting P ¹⁰ is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%.

The weight average molecular weight of the polymer chain represented by ^P10 is preferably 500 to 20,000. The lower limit is preferably 1,000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

The specific resin can be used as both a binder and a dispersant.

(Other resins)
The photocurable composition of the present invention may further contain a resin other than the specific resins described above (hereinafter, also referred to as "other resin").

As the other resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.

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

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

For the resin having an acid group, the description in paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding paragraphs 0685 to 0700 of the specification of US Patent Application Publication No. 2012/0235099) and the description in paragraphs 0076 to 0099 of JP 2012-198408 A can be referred to, and the contents of these are incorporated herein. In addition, a commercially available product can also be used as the resin having an acid group. In addition, there is no particular restriction on the method of introducing an acid group into the resin, but an example of the method is the method described in Japanese Patent No. 6349629 A. In addition, as a method of introducing an acid group into a resin, a method of reacting an acid anhydride with a hydroxyl group generated by a ring-opening reaction of an epoxy group to introduce an acid group can also be used.

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

Commercially available resins with basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24 000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be a block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A, a block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A, or a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP 2019-184763 A, the contents of which are incorporated herein by reference.

As the other resin, it is also preferable to use a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the photosensitive 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.

As another resin, it is also preferable to use a resin having an aromatic carboxy group. In a resin having an aromatic carboxy group, the aromatic carboxy group may be included in the main chain of a repeating unit, or may be included in a side chain of the repeating unit. The aromatic carboxy group is preferably included in the main chain of a repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In an aromatic carboxy group, the number of carboxy groups bonded to an 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.

As the other resin, it is preferable to use at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is blocked with an acid group. Such resins are preferably used as dispersants.

Examples of the graft polymer include resins having repeating units with graft chains. Examples of the graft chain include graft chains containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an alkylthioether group. Of these, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferred, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

Specific examples of graft polymers include the resins described in paragraphs 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A.

Star polymers include resins with a structure in which multiple polymer chains are bonded to a core. Specific examples of star polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962A.

The block copolymer is preferably a block copolymer of a block of a polymer having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A) and a block of a polymer having a repeating unit not containing an acid group or a basic group (hereinafter also referred to as block B). As the block copolymer, the block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A and the block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A can also be used, the contents of which are incorporated herein by reference.

Examples of resins in which at least one end of a polymer chain is blocked with an acid group include resins in which at least one end of a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure is blocked with an acid group. Examples of acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphate groups.

Other resins can also be used as dispersants. 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 when the total amount of the acid groups and the basic groups is 100 mol% is preferable. 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 the amount of acid groups is preferably a resin in which the total amount of the acid groups and the basic groups is 100 mol% is preferable. The basic group possessed by the basic dispersant is preferably an amino group.

Dispersants are also available as commercially available products. Specific examples include the Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), the Solsperse series manufactured by Lubrizol Japan (e.g., Solsperse 20000, 76500, etc.), the Ajisper series manufactured by Ajinomoto Fine-Techno Co., Ltd., A208F (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Sandet ET (manufactured by Sanyo Chemical Industries, 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.

The resin content in the total solid content of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.

The photocurable composition preferably contains 0.01 to 2 parts by mass of the specific compound described above per 100 parts by mass of resin. The upper limit is preferably 1.5 parts by mass or less, more preferably 1.2 parts by mass or less, and even more preferably 1 part by mass or less. The lower limit is preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more.

The content of the above-mentioned specific resin in the total solid content of the photocurable composition is preferably 1 to 50 mass%. The upper limit is preferably 40 mass% or less, and more preferably 30 mass% or less. The lower limit is preferably 5 mass% or more, and more preferably 10 mass% or more. The content of the above-mentioned specific resin in the resin contained in the photocurable composition is preferably 2 to 100 mass%, more preferably 5 to 100 mass%, and even more preferably 10 to 100 mass%.

The photocurable composition preferably contains 0.01 to 2 parts by mass of the specific compound described above per 100 parts by mass of the specific resin described above. The upper limit is preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. The lower limit is preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more.

The photocurable composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more types of resins are contained, it is preferable that the total amount of the resins is within the above range.

<<Photopolymerization initiator>>
The photocurable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet to visible regions is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the 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 a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 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, JP 2013-190459 JP-A-2020-172619, the polymer described in JP-A-2020-152120, the compound represented by formula 1 described in WO 2020/152120, the compound described in JP-A-2021-181406, the photopolymerization initiator described in JP-A-2022-013379, the compound represented by formula (1) described in JP-A-2022-015747, the fluorine-containing fluorene oxime ester photoinitiator described in JP-T-2021-507058, the compound 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 the publication, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 0062 of WO 2019/013112, 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-T-2022-515524. Initiators described in JP-T-2023-517304. Initiators described in Chinese Patent Application Publication No. 114149517, etc. are included.

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

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc. 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.

Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like. 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), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure 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 Examples of the oxime compound include G-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (all manufactured by TRONLY), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-014052). In addition, it is also preferable to use a compound that is not colorable or a compound that is highly transparent and does not easily discolor as the oxime compound. Examples of commercially available products include ADEKA ARCLES NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022/085485 can also be used.

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

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 heterocycle;
R ^1a represents a hydrogen atom or an acyl group;
^R2a represents an alkyl group or an aryl group;
R ^3a and R ^4a each independently represent a hydrogen atom or an alkyl group;
Alk ¹ and Alk ² each independently represent an alkyl group;
R ^3a and R ^4a may be bonded to form a ring;
Alk ¹ and Alk ² may be linked to form a ring;
n represents 0 or 1.

Examples of the divalent linking group represented by X ^1a in formula (OX-1) include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic 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. R ^x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

X ^1a in formula (OX-1) is preferably a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and further preferably a group represented by formula (X-2) or formula (X-6).
In the formula, R ^X1 to R ^X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and * represents a bond.

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

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

The number of carbon atoms in the alkynyl group represented by R ^X1 to R ^X9 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 heterocyclic group.

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

The heterocyclic group represented by R ^X1 to R ^X9 is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are 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 have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

In formula (OX-1), R ^1a represents a hydrogen atom or an acyl group, and is preferably an acyl group.
The acyl group represented by R ^1a is preferably a group represented by —C(O)—R ^101. R ¹⁰¹ represents an aryl group or a heterocyclic group, and is preferably an aryl group.

The number of carbon atoms of the aryl group represented by R ¹⁰¹ is preferably 6 to 20, and more preferably 6 to 12. 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 heterocyclic group. The aryl group represented by ^{R 101} is preferably a phenyl group, a methylphenyl group, or a naphthyl group, and more preferably a methylphenyl group or a naphthyl group.

The heterocyclic group represented by R ¹⁰¹ is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are 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 have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

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

In formula (OX-1), R ^3a and R ^4a each independently represent a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
The number of carbon atoms in the alkyl group represented by R ^3a and R ^4a is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
^R3a and ^R4a may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.

In formula (OX-1), Alk ¹ and Alk ² each independently represent 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.
^Alk1 and ^Alk2 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.

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

Specific examples of the compound represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of JP2012-113104A and the compounds described in paragraph 0041 of JP2012-189997A.

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

In formula (OX-2), R ^1b and R ^2b each independently represent a substituent, R ^3b to R ^7b each independently represent a hydrogen atom or a substituent, Ar ^1b represents an aromatic ring group or a heterocyclic group which may have a substituent, and n represents 0 or 1.

Examples of the substituent represented by R ^1b and R ^2b include an alkyl group and an aryl group, and an alkyl group is preferable. The number of carbon atoms of the alkyl group 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, an alkenyl group, an alkynyl group, and a heterocyclic group. The number of carbon atoms of the aryl group 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 heterocyclic group.

The substituents represented by R ^3b to R ^7b include a halogen atom, an alkyl group and an aryl group, the alkyl group and the aryl group being as described above.
R ^3b to R ^7b are preferably hydrogen atoms.

Ar ^1b represents an aromatic ring group or a heterocyclic group which may have a substituent, and Ar ^1b is preferably an aromatic ring group which may have a substituent. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. 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 preferable. Examples of the acyl group include the acyl groups described above.

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

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 to R ^3c each independently represent a substituent;
L ^1c represents a single bond or CR ^11c R ^12c , and R ^11c and R ^12c each independently represent a hydrogen atom, an alkyl group, or an aryl group;
X ^1c represents -CH ₂ -, -O- or -S-;
k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.

Examples of the substituent represented by R ^1c and R ^2c include an alkyl group and an aryl group, and an alkyl group is preferable. The number of carbon atoms of the alkyl group 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, an alkenyl group, an alkynyl group, and a heterocyclic group. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12, even 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 heterocyclic group.
R ^2c is preferably an alkyl group having a branched or cyclic structure.

Examples of the substituent represented by ^R3c 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 preferable. Examples of the acyl group include the acyl groups described above.

L ^1c represents a single bond or CR ^11c R ^12c , and R ^11c and R ^12c each independently represent a hydrogen atom, an alkyl group, or an aryl group. The alkyl group and aryl group in R ^11c and R ^12c have the same meaning as the alkyl group and aryl group in R ^1c and R ^2c . When k is 1, L ^1c is preferably a single bond.

X ^1c represents -CH ₂ -, -O- or -S-, and preferably -O- or -S-.

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

^Ar2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

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

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

As a photopolymerization initiator, it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and the storage stability of the photocurable composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.

The content of the photopolymerization initiator in the total solid content of the photocurable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

The photocurable composition preferably contains 0.1 to 40 parts by mass of the specific compound described above per 100 parts by mass of the photopolymerization initiator. The upper limit is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. The lower limit is preferably 0.2 parts by mass or more, and more preferably 0.5 parts by mass or more.

In the photocurable composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

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

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 from the standpoint of a wide range of color variations, ease of dispersion, safety, etc., it is preferable that the pigment is an organic pigment. The coloring material preferably contains a pigment.

The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and 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.

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

The specific surface area of the pigment is preferably 1 to 300 ^{m 2} /g. The lower limit is preferably 10 m ² /g or more, more preferably 30 m ² /g or more. The upper limit is preferably 250 m ² /g or less, more preferably 200 m ² /g or less. The value of the specific surface area can be measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method.

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

The red colorant may be a diketopyrrolopyrrole compound, anthraquinone compound, an azo compound, a naphthol compound, an azomethine compound, a xanthene compound, a quinacridone compound, a perylene compound, or a thioindigo compound, preferably a diketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound, more preferably a diketopyrrolopyrrole compound. The red colorant is preferably a pigment (red pigment), more preferably a diketopyrrolopyrrole pigment.

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, and 297. In addition, as a red colorant, a compound described in paragraph 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

As red colorants, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.

Green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

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. In addition, 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 in one molecule can also be used as green colorants. Specific examples include compounds described in WO 2015/118720. In addition, compounds described in paragraph 0029 of WO 2022/085485, aluminum phthalocyanine compounds described in JP 2020-070426 A, and diarylmethane compounds described in JP 2020-504758 A can also be used as green colorants.

Preferred green colorants are C.I. Pigment Green 7, 36, 58, 62, and 63.

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

Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include C.I. 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 other yellow pigments.

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

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

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

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

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

A dye polymer can also be used as a chromatic colorant. The dye polymer is preferably a dye dissolved in a solvent. The dye polymer may form particles. When the dye polymer is a particle, it is usually used in a state of being dispersed in a solvent. A particulate dye polymer can be obtained, for example, by emulsion polymerization, and examples of the compound and manufacturing method described in JP-A-2015-214682 include the compound and manufacturing method described in JP-A-2015-214682. The dye polymer has two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular limit to the upper limit, but it 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 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. The dye multimer may be a compound described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, WO2016/031442, etc.

As chromatic colorants, there may be mentioned a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP 2020-117638 A, a phthalocyanine compound described in WO 2020/174991 A, an isoindoline compound or a salt thereof described in JP 2020-160279 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A, Compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by 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, may be used in the rod-shaped structure, or may be used 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, compounds described in JP-A-2022-045895, compounds described in WO 2022/050051, compounds described in JP-A-2020-090676, compounds described in JP-A-2020-055956, compounds described in JP-A-2021-031681, compounds described in JP-A-2022-056354 Compounds described in US Patent Application Publication No. 2021/0355327, compounds described in WO 2022/065357, compounds described in JP 2020-045436, compounds described in Korean Patent Publication No. 10-2021-0146726, compounds described in JP 2018-178039, compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in JP 2022-104822, compounds described in JP 2022-096701, compounds described in JP 2020-023652, 80 of the Journal of the Color Materials Association (published in 2022) Green pigments described on pages 1 to 84, compounds described in JP 2022-143135 A, compounds described in JP 2022-140287 A, compounds described in WO 2022/136308 A, perylene compounds described in Chinese Patent Application Publication No. 113061349 A, cyan pigments described in Korean Patent Publication No. 10-2017-0018993 A, isoindoline compounds described in JP 2020-180176 A, compounds described in JP 2023-013209 A, compounds described in JP 2023-013166 A, xanthene compounds described in WO 2023/286526 A, compounds described in JP 2021-155746 A, compounds described in JP 2021-155747 A, JP 2021-15 Compounds described in JP-A-2021-155748, compounds described in JP-A-2021-155749, compounds described in WO 2018/051876, compounds described in JP-A-2020-083981, compounds described in JP-A-2023-056463, compounds described in JP-T-2023-515473, dioxane compounds described in JP-T-2022-549530 It is also possible to use the compound described in JP-A-2022-061494, the pigment preparation described in JP-A-2023-057917, the diketopyrrolopyrrole pigment described in JP-A-2023-061273, the phthalocyanine described in JP-T-2023-519314, and the quinophthalone described in JP-A-2023-080419.

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

(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. The white coloring material can be the white pigment described in paragraphs 0040 to 0043 of WO 2022/085485.

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

Examples of inorganic black coloring materials include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferred. As titanium black, titanium black described in paragraph 0044 of WO 2022/085485 can be used. As an inorganic black coloring material, zirconium nitride powder described in JP 2023-048173 A can also be used.

Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. As the organic black colorant, the compounds described in paragraph number 0166 of International Publication No. 2022/065215 can be used. In addition, as the organic black colorant, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of JP-A-2017-226821 and black azo pigments described in JP-A-2022-121935 may also be used.

The black coloring materials described in the Journal of the Japan Color Materials Association, Vol. 96, No. 9, 2023, pages 294-307 can also be used.

(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 range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1000 nm. In addition, the ratio A ¹ /A ^{2 between the absorbance A 1 at} a wavelength of 500 nm of the infrared absorbing colorant and the absorbance A ² at the maximum absorption wavelength is preferably 0.08 or less, more preferably 0.04 or less. In addition, the infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

Infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, 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 compound described in paragraph 0121 of WO 2022/065215, the squarylium compound described in JP 2020-075959 A, the copper complex described in Korean Patent Publication No. 10-2019-0135217 A, the croconic acid compound described in JP 2021-195515 A, the infrared absorbing dye described in JP 2022-022070 A, and the compound described in WO 2019/021767 A. , compounds described in JP-A-2019-127549, compounds described in WO 2022/059619, 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, compounds described in WO 2020/218615, diiminium compounds described in JP 2023-068643 A, squarylium compounds described in JP 2023-052770 A, phthalocyanine compounds described in Korean Patent Publication No. 10-2022-0163680, indigo monoboron complexes described in JP 2023-073064 A, and JP 2023-073064 A. Phthalocyanine compounds described in JP 23-066025 A, 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 can also be used.

The content of the colorant in the total solid content of the photocurable composition is preferably 30 to 80% by mass. The upper limit is preferably 70% by mass or less, and more preferably 65% by mass or less. The lower limit is preferably 35% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more.

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

The pigment content 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.

In the photocurable composition of the present invention, only one type of colorant 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.

<<Ammonium cation compound (compound having quaternary ammonium cation)>>
The photocurable composition of the present invention preferably contains a compound having a quaternary ammonium cation. According to this embodiment, the adhesion and solvent resistance of the obtained film can be further improved. Hereinafter, the compound having a quaternary ammonium cation is also referred to as an ammonium cation compound.

The ammonium cation compound may be a low molecular weight compound or a high molecular weight compound. A low molecular weight compound and a high molecular weight compound may be used in combination. When a low molecular weight compound and a high molecular weight compound are used in combination, the ratio is preferably 0.1 to 15 parts by mass of the low molecular weight compound per 100 parts by mass of the high molecular weight compound. The upper limit is preferably 12 parts by mass or less, and more preferably 10 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more.

If the ammonium cation compound is a low molecular weight compound, its molecular weight is preferably 600 or less, and more preferably 450 or less.

The low molecular weight ammonium cation compound is preferably a salt of an ammonium cation and an anion.

The ammonium cation includes a cation represented by the formula (Am-1).
In formula (Am-1), R ^Am1 to R ^Am4 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group, and a hydrogen atom contained therein may be substituted with -OH, -OCO-CH=CH ₂ , or -OCO-CH=CHR _b . In addition, -O-, -S-, -CO-, -NH-, or -NR _b - may be inserted between the carbon-carbon bonds of the alkyl group and the alkenyl group. In addition, R ^Am1 to R ^Am4 may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. In this case, a hydrogen atom contained in the heterocycle may be substituted with -R _b or -OH. R _b represents an alkyl group having 1 to 10 carbon atoms.

Specific examples of ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, monoethyltrimethylammonium cation, monopropyltrimethylammonium cation, monobutyltrimethylammonium cation, monostearyltritylammonium cation, distearyldimethylammonium cation, tristearylmonomethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, dioctyldimethylammonium cation, monolauryltrimethylammonium cation, dilauryldimethylammonium cation, trilaurylmethylammonium cation, triamylbenzylammonium cation, trihexylbenzylammonium cation, trioctylbenzylammonium cation, trilaurylbenzylammonium chloride cation, benzyldimethylstearylammonium cation, benzyldimethyloctylammonium cation, dialkyl (alkyl is C14 to C18) dimethylammonium cation, and cations having the structure shown below.

Anions that form salts with ammonium cations include halide anions, hydroxide anions, alkoxide anions, phenoxide anions, amide anions (including amides substituted with acyl groups or sulfonyl groups), imide anions (including imides substituted with acyl groups or sulfonyl groups), anilide anions (including anilides substituted with acyl groups or sulfonyl groups), thiolate anions, hydrogen carbonate anions, carboxylate anions, thiocarboxylate anions, dithiocarboxylate anions, hydrogen sulfate anions, sulfonate anions, dihydrogen phosphate anions, phosphate diester anions, phosphonate monoester anions, hydrogen phosphonate anions, phosphinate anions, nitrogen-containing heterocyclic anions, nitrate anions, hypochlorite anions, cyanide anions, cyanate anions, isocyanate anions, thiocyanate anions, isothiocyanate anions, and azide anions.

The ammonium cation compound may be a compound having a betaine structure having a quaternary ammonium cation moiety and an anion moiety in the same molecule. An example of the structure is a structure in which any hydrogen atom in the group represented by R ^Am-4 in the above formula (Am-1) is substituted with an anion moiety. Examples of the anion moiety include the above anions, with a carboxylate anion being preferred.

When the compound having a quaternary ammonium cation is a polymeric compound, its weight average molecular weight is preferably 2,000 to 50,000. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. The upper limit is preferably 40,000 or less, and more preferably 30,000 or less.

The ammonium cationic compound, which is a polymeric compound, is preferably a salt of a polymer having a quaternary ammonium cationic group and an anion. Such an ammonium cationic compound is also a material that corresponds to a resin.

Anions include those mentioned above.

The quaternary ammonium cationic group contained in the polymer is preferably a group represented by formula (Cat-1).

In the formula, R ^cat1 to R ^cat3 each independently represent an alkyl group or an aryl group, and * represents a bond.

The number of carbon atoms in the alkyl group represented by R ^cat1 to R ^cat3 is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5. The alkyl group represented by R ^cat1 to R ^cat3 is preferably linear or branched, and more preferably linear.
The aryl group represented by R ^cat1 to R ^cat3 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.

It is preferable that R ^cat1 to R ^cat3 are each independently an alkyl group. It is preferable that R ^cat1 and R ^cat2 are each independently an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. It is preferable that ^{R cat3} is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The polymer having a quaternary ammonium cationic group is preferably a polymer having a quaternary ammonium cationic group on the side chain.

The weight average molecular weight of the polymer having a quaternary ammonium cationic group is preferably 2,000 to 50,000. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. The upper limit is preferably 40,000 or less, and more preferably 30,000 or less.

The content of the ammonium cationic compound in the total solid content of the photocurable composition is preferably from 0.1 to 40% by mass.
In addition, when the ammonium cationic compound is a low molecular weight compound, the content of the ammonium cationic compound in the total solid content of the photocurable composition is preferably 0.1 to 10 mass %, the upper limit is preferably 8 mass % or less, and more preferably 5 mass % or less, and the lower limit is preferably 0.2 mass % or more, and more preferably 0.5 mass % or more.
In addition, when the ammonium cationic compound is a polymeric compound, the content of the ammonium cationic compound in the total solid content of the photocurable composition is preferably 5 to 40 mass %, the upper limit is preferably 35 mass % or less, and more preferably 30 mass % or less, and the lower limit is preferably 10 mass % or more, and more preferably 15 mass % or more.

In the photocurable composition of the present invention, only one type of ammonium cation 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 within the above range.

<<Solvent>>
The photocurable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, refer to paragraph 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference. In addition, 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, propylene glycol dimethyl ether, butyl acetate ... Examples of the 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 and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, there are cases where it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

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, organic solvents with metal contents at the ppt (parts per trillion) by mass level may be used, and such organic solvents are provided, for example, by Toyo Gosei (The Chemical Daily, November 13, 2015).

Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The filter used for filtration preferably has a pore size of 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.

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

The peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

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

From the viewpoint of environmental regulations, it is preferable that the photocurable composition of the present invention is substantially free of environmentally regulated substances. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally regulated 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 and handling methods are strictly regulated. These compounds may be used as solvents when producing each component used in the photocurable composition, and may be mixed into the photocurable composition as a residual solvent. From the viewpoint of human safety and environmental consideration, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally regulated substances, a method of reducing the environmentally regulated substances by heating or reducing the pressure in the system to a temperature above the boiling point of the environmentally regulated substances and distilling off the environmentally regulated substances from the system can be mentioned. In addition, 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. In addition, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added and then distilled off under reduced pressure in order to suppress the radical polymerization reaction from proceeding during distillation under reduced pressure and causing crosslinking between molecules. These distillation methods can be used at any stage, such as the stage of the raw materials, the stage of the product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the photocurable composition prepared by mixing these compounds.

<<Pigment derivatives>>
The photocurable composition of the present invention may contain a pigment derivative. The pigment derivative is used as a dispersing aid. The dispersing aid is a material for enhancing the dispersibility of a coloring material such as a pigment in the photocurable composition. The pigment derivative may be 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.

The above dye structures 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.

Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imide acid group, and salts thereof. Examples of atoms or atomic groups constituting the salt include an alkali metal ion (Li ⁺ , Na ⁺ , K ⁺ , etc.), an alkaline earth metal ion (Ca ²⁺ , Mg ²⁺ , etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. Examples of the carboxylic acid amide group include a group represented by -NHCOR ^X1 . Examples of the sulfonamide group include a group represented by -NHSO ₂ R ^X2 . Examples of the imide acid group include a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 , or -SO ₂ NHCOR ^X6 , and more preferably -SO ₂ NHSO ₂ R ^X3 . R ^x1 to R ^x6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^x1 to R ^x6 may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom.

Basic groups include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Atoms or atomic groups that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include the compounds described in paragraphs 0037 to 0054 of WO 2016/035695, the compounds described in paragraphs 0061 to 0086 of WO 2017/146092, the compounds described in paragraphs 0017 to 0068 of WO 2018/230387, the compounds described in paragraphs 0085 to 0099 of WO 2020/054718, the compounds described in paragraph 0099 of WO 2020/054718, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6,996,282.

The content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. The photocurable composition may contain only one type of pigment derivative, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.

<<Polyalkyleneimine>>
The photocurable composition of the present invention may also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid for pigments. 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 number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

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. In addition, when the molecular weight value of the polyalkyleneimine 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, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number average molecular weight value measured by the boiling point elevation method is used. In addition, when the 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. In addition, when the molecular weight cannot be measured by the viscosity method or is difficult to measure by the viscosity method, the number average molecular weight value measured in polystyrene equivalent value by GPC (gel permeation chromatography) method is used.

The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.

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

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

<<Compound Having Cyclic Ether Group>>
The photocurable composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group means 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 the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more.

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

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

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

The content of the compound having a cyclic ether group in the total solid content of the photocurable composition is preferably 0.1 to 20 mass%. The lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more. The upper limit is preferably 15 mass% or less, and more preferably 10 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 is within the above range.

<<Curing accelerator>>
The photocurable composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. Specific examples of the curing accelerator include the compounds described in paragraph 0164 of International Publication No. 2022/085485 and the compounds described in JP-A-2021-181406. The content of the curing accelerator in the total solid content of the photocurable composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

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

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

<<Silane coupling agents>>
The photocurable composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and it is preferable that the silane coupling agent is a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate 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, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, 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, and an amino group, a (meth)acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include the compound described in paragraph 0177 of International Publication No. 2022/085485 and the compound described in JP-A-2019-183020. The content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The silane coupling agent may be one type or two or more types. In the case of two or more types, it is preferable that the total amount is within the above range.

<<Surfactants>>
The photocurable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For 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.

As fluorosurfactants, the compounds described in paragraphs 0167 to 0173 of WO 2022/085485 can be used.

Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.

Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), 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), etc. In addition, a compound having the following structure can also be used as the silicone surfactant.

The content of the surfactant in the total solid content of the photocurable composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% by mass to 3.0% by mass. There may be only one type of surfactant, or two or more types. When there are two or more types, it is preferable that the total amount is within the above range.

<<Antioxidants>>
The photocurable composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenol-based antioxidant include hindered phenol compounds. The phenol-based antioxidant is preferably a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group. The aforementioned 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, Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-50F, Adeka STAB AO-60, Adeka STAB AO-60G, Adeka STAB AO-80, Adeka STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidant is a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. WO 2017/006600, a compound described in International Publication No. WO 2017/164024, and a compound described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the photocurable composition is preferably 0.01 to 20 mass%, more preferably 0.3 to 15 mass%. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Other ingredients>>
The photocurable composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, 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.

The photocurable 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 , and SiO ₂ . The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

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

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

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

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

From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be restricted. In the photocurable composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) and its salts, and perfluoroalkylcarboxylic acid (particularly perfluoroalkyl carboxylic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) and its salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solid content of the photocurable composition. The photocurable composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. For example, by using a compound that can be a substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can be a substitute for perfluoroalkyl carboxylic acid and its salt, a photocurable composition that is substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected. Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from the scope of regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The photocurable composition of the present invention may contain perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.

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

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

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

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

It is preferable that the preparation of the photocurable composition 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 bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In addition, when grinding the pigment in a sand mill (bead mill), it is preferable to use small-diameter beads and increase the bead packing rate to perform processing under conditions that increase the grinding efficiency. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the grinding process. In addition, the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Information Technology Co., Ltd., July 15, 2005" or "Dispersion Technology and Industrial Application Practice Focused on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978", and in paragraph number 0022 of JP 2015-157893 A. In addition, in the process for dispersing the pigment, a salt milling process may be performed to refine the particles. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in, for example, JP 2015-194521 A and JP 2012-046629 A may be referred to. Examples of materials for the beads used for 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 with a Mohs hardness of 2 or more. The photocurable composition may contain 1 to 10,000 ppm of the above beads.

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

<Membrane>
The film of the present invention is obtained from the above-mentioned photocurable composition of the present invention. The film of the present invention can be used for optical filters such as color filters, infrared transmission filters, and infrared cut filters.

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 film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

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

<Membrane manufacturing method>
Next, a method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the photocurable composition of the present invention. The film production method preferably further includes a step of forming a pattern (pixel). An example of a method for forming the pattern (pixel) is photolithography.

Pattern formation by photolithography preferably includes a step of forming a composition layer on a support using the photocurable composition of the present invention, a step of exposing the composition layer to light in a pattern, and a step of developing and removing the unexposed parts of the composition layer to form a pattern (pixels). If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming the composition layer, the photocurable composition of the present invention is used to form a composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, and a silicon substrate is preferable. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. The silicon substrate may also be formed with a black matrix that isolates each pixel. The silicon substrate may also be provided with a base layer to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferable that the surface contact angle is 30 to 80° when measured with water.

　A known method can be used as a method for applying the photocurable 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, a method described in JP 2009-145395 A); various printing methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; and a nanoimprint method. In addition, the application method described in paragraph 0207 of WO 2022/085485 can also be used.

The composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and even more preferably 110°C or less. The lower limit can be, for example, 50°C or more, and can also be 80°C or more. 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, etc.

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

Radiation (light) that can be used for exposure includes g-line and i-line. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wavelength light sources of 300 nm or more can also be used.

In addition, during exposure, light may be applied continuously or in pulses (pulse exposure). Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ^2. The oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, for example, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or exposure may be performed under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). The exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m ² to 100,000 W/m ² (e.g., 5,000 W/m ² , 15,000 W/m ² , or 35,000 W/m ² ). The oxygen concentration and exposure illuminance may be appropriately combined. For example, the oxygen concentration can be 10% by volume and the illuminance can be 10,000 W/m ² , and the oxygen concentration can be 35% by volume and the illuminance can be 20,000 W/m ² .

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

The developer may be an organic solvent or an alkaline developer, with an alkaline developer being preferred. The developer and the washing (rinsing) method after development may be as described in paragraph 0214 of WO 2022/085485.

After development and drying, it is preferable to perform additional exposure processing or heating processing (post-baking). Additional exposure processing and post-baking are curing processing after development to 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, a convection oven (hot air circulation dryer), or a high-frequency heater to achieve the above conditions for the developed film. When additional exposure processing is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. In addition, additional exposure processing may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

<Optical filter>
The film of the present invention can be used for an optical filter. The types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and are preferably color filters. The color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as its color pixel.

The optical filter may have a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity/hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, infrared rays, etc.) can be imparted. 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 forming the protective layer by 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. The components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , and Si ₂ N ₄ , and may contain two or more of these components. For example, in the case of a protective layer intended for oxygen blocking, the protective layer preferably contains a polyol resin, SiO ₂ , and Si ₂ N _4. In addition, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.

When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet can be used as a method for applying the resin composition for forming the protective layer. 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 for forming the protective layer. 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.

The protective layer may contain additives such as organic or inorganic fine particles, absorbents for light of specific wavelengths (e.g., ultraviolet light, infrared light, etc.), refractive index adjusters, antioxidants, adhesion agents, and surfactants, as necessary. Examples of organic or inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbents can be used as absorbents for light of specific wavelengths. 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, based on the total mass of the protective layer.

The protective layer may be the one described in paragraphs 0073 to 0092 of JP2017-151176A.

The optical filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example in a grid pattern.

<Solid-state imaging element>
The solid-state imaging device of the present invention has the above-mentioned 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, and examples thereof include the following configurations.

The substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and a transfer electrode made of polysilicon or the like, a light-shielding film on the photodiodes and the transfer electrode with only the light receiving portion of the photodiode open, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter on the device protection film. Furthermore, the device protection film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protection film and below the color filter (the side closer to the substrate), or a light-collecting means on the color filter. The color filter may have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a lattice shape. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018/043654 A. In addition, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance. The 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.

<Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. Examples of the image display device include liquid crystal display devices and organic electroluminescence display devices. The definition of the image display device and details of each image display device are described, for example, in "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990)" and "Display Devices (by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)". In addition, the liquid crystal display device is described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". There is no particular limitation 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 "Next Generation Liquid Crystal Display Technology".

The present invention will be specifically explained below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Note that Ph in the structural formula shown below is a phenyl group.

<Evaluation of Resin>
(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the resin was calculated by GPC (Gel Permeation Chromatography) measurement under the following measurement conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Precolumn: TSKGUARDCOLUMN MP(XL) 6mm x 40mm (manufactured by Tosoh Corporation)
Sample column: The following four columns are directly connected (all manufactured by Tosoh Corporation):
TSK-GEL Multipore-HXL-M 7.8mm x 300mm
Reference column: same as sample column Thermostat temperature: 40°C
Mobile phase: tetrahydrofuran Sample side mobile phase flow rate: 1.0 mL/min Reference side mobile phase flow rate: 0.3 mL/min Sample concentration: 0.1% by mass
Sample injection volume: 100 μL
Data collection time: 16 to 46 minutes after sample injection Sampling pitch: 300 ms (milliseconds)

(Acid value)
The acid value of the resin was determined by neutralization titration using an aqueous solution of sodium hydroxide. Specifically, the obtained resin was dissolved in a solvent, and the solution was titrated with an aqueous solution of sodium hydroxide using a potentiometric method to calculate the number of millimoles of acid contained in 1 g of solid content of the resin, and then the value was multiplied by the molecular weight of potassium hydroxide (KOH), which is 56.1.

(C=C value (ethylenically unsaturated bond-containing group value))
The C═C value (ethylenically unsaturated bond-containing group value) of the resin was calculated from the raw materials used in the synthesis of the resin.

<Preparation of resin solution>
[Production Example 1-1] Production of resin solution (B-1) A separable flask with a cooling tube was prepared as a reaction vessel, and on the other hand, as a monomer dropping vessel, 162.38 parts by mass of benzyl methacrylate (hereinafter referred to as "BzMA"), 34.00 parts by mass of methacrylic acid (hereinafter referred to as "MAA"), 6.06 parts by mass of 2,2'-azobis (2-methylpropionate) dimethyl (low metal grade) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "V-601HP"), 435 parts by mass of cyclohexanone, and 5.33 parts by mass of n-dodecanethiol (hereinafter referred to as "n-DM") were thoroughly stirred and mixed. 49 parts by mass of cyclohexanone was charged into the reaction vessel, and after nitrogen replacement, the temperature of the reaction vessel was heated in an oil bath with stirring to 75 ° C. After the temperature of the reaction vessel was stabilized at 75° C., dropping from the monomer dropping vessel to the reaction vessel was started. Dropping was carried out over 150 minutes while maintaining the temperature at 75° C. 120 minutes after the end of dropping, the temperature was raised to 90° C. After maintaining the temperature at 90° C. for 2 hours, the reaction solution was cooled to room temperature.
After the polymerization reaction was completed, 3.09 parts by mass of N,N-dimethyldodecylamine as an amine compound and 0.5 parts by mass of p-methoxyphenol as a polymerization inhibitor were added under air, and then 37.43 parts by mass of glycidyl methacrylate (hereinafter referred to as "GMA") and 96 parts by mass of cyclohexanone were added. Thereafter, the temperature of the reaction solution was started to be raised to 90°C. After maintaining 90°C for 6 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was discharged into a mixed liquid of 10,000 parts by mass of methanol and 2,500 parts by mass of water, and the precipitated solid (polymer) was filtered, and the filtered solid was washed twice with 500 parts by mass of water. The solid after washing was blown and dried at 50°C for 18 hours to obtain a resin B-1 having the following structure. The resulting resin B-1 had a weight average molecular weight (Mw) of 12,000, an acid value of 32 mgKOH/g, and a C=C value of 1.13 mmol/g.
Resin B-1 obtained by the above procedure was added to propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and the resin concentration (solid content concentration) of the final resin solution was adjusted to 30%, thereby producing a resin solution (B-1).

[Production Example 1-2] Production of resin solution (B-2) A separable flask with a cooling tube was prepared as a reaction vessel, and on the other hand, as a monomer dropping vessel, 30.7 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 43.1 parts by mass of MAA, 14.3 parts by mass of methyl methacrylate (hereinafter referred to as "MMA"), 113.5 parts by mass of BzMA, 4 parts by mass of benzoyl peroxide (hereinafter referred to as "PBO"), and 60 parts by mass of diethylene glycol dimethyl ether (hereinafter referred to as "DMDG") were prepared by stirring and mixing, and as a chain transfer agent dropping vessel, 8 parts by mass of n-DM and 32 parts by mass of DMDG were prepared by stirring and mixing. 375 parts by mass of DMDG were charged into the reaction vessel, and after nitrogen replacement, the temperature of the reaction vessel was heated in an oil bath while stirring to raise the temperature to 90 ° C. After the temperature of the reaction vessel was stabilized at 90°C, the dropping from the monomer dropping vessel and the chain transfer agent dropping vessel to the reaction vessel was started. The dropping was carried out over 135 minutes, while the temperature was kept at 90°C. 60 minutes after the dropping was completed, the temperature was raised to 110°C. After maintaining 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of oxygen/nitrogen=5/95 (v/v) mixed gas was started. Next, 50.9 parts by mass of GMA, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol) (hereinafter referred to as "MBMTB"), and 0.8 parts by mass of triethylamine (hereinafter referred to as "TEA") were charged into the reaction vessel, and the reaction was carried out at 110°C for 3 hours. After confirming the completion of the reaction by measuring the acid value of the reaction solution, 155 parts by mass of DMDG was added to the reaction solution and cooled to room temperature. To the cooled reaction solution, 1000 parts by mass of water was added, and the precipitated solid (polymer) was filtered off, and the filtered solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water to obtain Resin B-2 having the following structure: The weight average molecular weight (Mw) of the obtained Resin B-2 was 18000, the acid value was 32 mgKOH/g, and the C=C value was 1.42 mmol/g.
Resin B-2 obtained by the above procedure was added to PGMEA, and the resin concentration (solid content concentration) of the finally obtained resin solution was adjusted to 30%, thereby producing a resin solution (B-2).

[Production Example 1-3] Production of resin solution (B-3) Into a three-neck flask, 30.4 parts by mass of a macromonomer represented by the following formula (MM), 51 parts by mass of ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300, manufactured by Toagosei Co., Ltd.), and PGMEA were introduced to obtain a mixture. The mixture was stirred while blowing in nitrogen.
Next, the mixture was heated to 75°C while flowing nitrogen gas into the flask. Next, 0.82 parts by mass of n-DM and then 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the mixture to initiate the polymerization reaction. After heating the mixture at 75°C for 2 hours, 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) were further added to the mixture. After 2 hours, 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) were further added to the mixture. After another 2 hours of reaction, the mixture was heated to 90°C and stirred for 3 hours. The polymerization reaction was terminated by the above operation. After the polymerization reaction was completed, 9.6 parts by mass of dimethyldodecylamine as an amine compound and 0.3 parts by mass of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a polymerization inhibitor were added in air, and then 9 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) was added dropwise.
After the dropwise addition, the reaction was continued in air at 90°C for 24 hours, and the completion of the reaction was confirmed by measuring the acid value, and the reaction solution was cooled to room temperature. 1000 parts by mass of water was added to the cooled reaction solution, and the precipitated solid (polymer) was filtered out. The filtered solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water to obtain Resin B-3 having the following structure. The weight average molecular weight (Mw) of the obtained Resin B-3 was 17200, the acid value was 70 mgKOH/g, and the C=C value was 0.50 mmol/g.
Resin B-3 obtained by the above procedure was added to PGMEA, and the resin concentration (solid content concentration) of the finally obtained resin solution was adjusted to 30%, thereby producing a resin solution (B-3).

[Production Example 1-4] Production of resin solution (B-4) 8 parts by mass of 3-mercapto-1,2-propanediol, 12 parts by mass of pyromellitic anhydride, 80 parts by mass of PGMEA, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 30 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, 10 parts by mass of ethyl acrylate, 5 parts by mass of methacrylic acid, 10 parts by mass of benzyl methacrylate, and 35 parts by mass of 2-hydroxyethyl methacrylate were charged, and the inside of the reaction vessel was heated to 80 ° C., and 1 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by solid content measurement that 95% had reacted. Next, the flask was purged with air, and 35.0 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.1 parts by mass of hydroquinone were charged and reacted at 70°C for 4 hours (third step). After confirming by infrared absorption spectroscopy that the peak at 2270 cm ^-1 due to the isocyanate group had disappeared, the reaction solution was cooled to obtain resin B-4 having the following structure. The acid value of the obtained resin B-4 was 40 mgKOH/g, the weight average molecular weight was 12000, and the C=C value was 1.44 mmol/g.
In formula (B-4), either *1 or *2 is bonded to *5 or *6 to form a polyester main chain, and the other is bonded to *3 or *4 to form a polyester main chain. Either *3 or *4 is bonded to *1 or *2 to form a polyester main chain, and the other is bonded to an OH group to form a carboxylic acid. Either *5 or *6 is bonded to *1 or *2 to form a polyester main chain, and the other is bonded to an OH group to form a carboxylic acid.

The resin B-4 obtained by the above procedure was added to PGMEA, and the resin concentration (solids concentration) of the final resin solution was adjusted to 30% to produce resin solution (B-4).

[Production Example 1-5] Production of resin solution (B-5) According to the synthesis method of resin (B3-1) solution described in paragraph 0350 of JP 2023-050814 A, resin B-5 having the following structure was obtained. The amine value of the obtained resin B-5 was 170 mgKOH/g and the weight average molecular weight was 20,000.
Resin B-5 obtained by the above procedure was added to PGMEA, and the resin concentration (solid content concentration) of the finally obtained resin solution was adjusted to 30%, thereby producing a resin solution (B-5).

<Production of finely divided pigment>
[Production Example 2-1]
(Production of finely divided pigment (PR254M))
100 parts by mass of C.I. Pigment Red 254 (BASF "B-CF"), 1200 parts by mass of sodium chloride, and 120 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 4 hours at 60 ° C. The obtained kneaded composition was added to 3000 parts by mass of warm water, stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day to obtain a finely divided pigment (PR254M).

[Production Examples 2-2 to 2-14]
Each finely divided pigment was obtained by carrying out the same process as in Production Example 2-1 above, except that the pigment used in Production Example 2-1 was changed from Pigment Red 254 to the pigments shown in the table below.

<Production of Pigment Dispersion>
[Production Examples 3-1 to 3-19]
The materials shown in the table below were mixed and then dispersed for 3 hours in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The resulting mixture was then filtered through a filter with a pore size of 5.0 μm to produce a pigment dispersion.

(Micronized pigment)
PR254M, PR272M, PY139M, PY150M, PY185M, PG59M, PG58M, PG36M, PG7M, PB15:6M, PB15:4M, PB15:6M, PV23M, PPB001M, SQ001M: finely divided pigments produced in Production Examples 2-1 to 2-14 described above. TiB: titanium oxynitride particles (manufactured by Mitsubishi Materials Electronic Chemicals).
CB: Carbon black particles (manufactured by Cabot, average primary particle diameter 15 nm)
ZrO ₂ : Zirconium oxide particles (manufactured by Nippon Denko Co., Ltd., average primary particle diameter 20 nm)
TiO ₂ : Titanium oxide particles (manufactured by Ishihara Sangyo Kaisha, Ltd., TTO-51(C), average primary particle size 10 to 30 nm, surface treated with alumina and stearic acid)

(derivative)
Derivatives 1 to 4: Compounds having the following structures

(Resin solution)
B-3 to B-5: Resin solutions (B-3) to (B-5) produced in the above-mentioned Production Examples 1-3 to 1-5

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)

<Preparation of Photocurable Composition>
The raw materials shown in the table below were mixed and stirred until homogeneous, and then filtered through a filter having a pore size of 1 μm to produce a photocurable composition.

In the table above, the abbreviations for various materials stand for the following:

(Pigment Dispersion)
DisR01, DisR02, DisY01, DisY02, DisY03, DisG01, DisG02, DisG03, DisG04, DisB01, DisB02, DisB03, DisV01, DisIR01, DisIR02, DisK01, DisK02, DisW01, DisW02: pigment dispersions produced in the above-mentioned Production Examples 3-1 to 3-19

(dye)
DyeM01: Dye having the following structure (weight average molecular weight 10,400, acid value 69 mgKOH/g, m: 4, n: 2)
DyeB01: Dye having the following structure (weight average molecular weight: 30,000)
DyeIR01: a dye having the following structure

(Resin solution)
B-1 to B-2: Resin solutions (B-1) to (B-2) produced in the above-mentioned Production Examples 1-1 and 1-2

(Specific compound)
A compound having the following structure:

(Polymerizable compound)
M-1: ARONIX M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass.)
M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide modified pentaerythritol tetraacrylate)
M-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid modified acrylic oligomer)

(Photopolymerization initiator)
I-1: Compound having the following structure
I-2: Adeka Arcles NCI-730 (manufactured by ADEKA Corporation)
I-3: Compound having the following structure

(Ultraviolet absorber)
U-1: Uvinul 3050 (manufactured by BASF, a benzophenone compound)
U-2: Adeka STAB LA-F70 (manufactured by ADEKA CORPORATION, triazine compound)
U-3: Adeka STAB LA-31RG (manufactured by ADEKA CORPORATION, benzotriazole compound)

(Polymerization inhibitor)
IN-1: p-Methoxyphenol IN-2: 2,2,6,6-Tetramethylpiperidine 1-oxyl free radical IN-3: Adeka STAB AO-80 (manufactured by ADEKA Corporation)

(Surfactant)
W-1: Compound having the following structure (silicone surfactant, number average molecular weight 1800)
W-2: Megafac F-781F (manufactured by DIC Corporation, fluorosurfactant)

(Quaternary ammonium salt compounds)
AN-1: Compound having the following structure
AN-2: Tetrabutylammonium bromide AN-3: (CH ₃ ) ₃ N ⁺ CH ₂ CO ₂ ^-

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: 1-methoxy-2-propanol (PGME)
S-3: Cyclopentanone

<Evaluation of Adhesion>
Each photocurable composition was spin-coated onto an 8-inch (1 inch is 2.54 cm) silicon wafer sprayed with hexamethyldisilazane so that the film thickness after formation was 0.8 μm, and heated for 2 minutes at 100° C. Next, using a KrF scanner exposure machine, the wafer was irradiated with KrF rays through a mask having an island pattern of 1.1 μm square at an illuminance of 35,000 W/m ² and an exposure dose of 200 mJ/cm ² .
Next, puddle development was carried out using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) at 25° C. for 40 seconds, followed by rinsing with running water for 30 seconds and spray drying to form a pattern (pixels).
The obtained pixels were observed from above using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) to measure the pixel pattern size. In addition, the adhesion was evaluated using an optical microscope. The pattern size when all pixels were in close contact was evaluated on a 5-point scale according to the following evaluation criteria.
-Evaluation criteria-
A: The pattern size is 0.9 μm or more and less than 1.0 μm, and all pixels are in close contact.
B: The pattern size is 1.0 μm or more and less than 1.05 μm, and all pixels are in close contact.
C: The pattern size is 1.05 μm or more and less than 1.1 μm, and all pixels are in close contact.
D: If the pattern size is not 1.1 μm or more, all pixels do not come into contact.

<Evaluation of Solvent Resistance>
An 8-inch (20.32 cm) silicon wafer was coated with a composition for forming an underlayer (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) using a spin coater so that the thickness after post-baking would be 0.1 μm, and the wafer was heated at 220° C. for 300 seconds using a hot plate to form an underlayer, thereby obtaining a silicon wafer (support) with an underlayer. Next, each photocurable composition was coated by spin coating so that the film thickness after post-baking would be 0.5 μm. Next, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, the obtained composition layer was exposed to light (KrF line) with a wavelength of 248 nm using a KrF scanner exposure machine at an illuminance of 35,000 W/m ² and an exposure dose of 200 mJ/cm ² . Next, the silicon wafer on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and paddle-treated with a 60% diluted solution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) at 23°C for 60 seconds, then fixed to the horizontal rotating table by a vacuum chuck system, and while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device, pure water was supplied in a shower-like manner from a spray nozzle from above the center of rotation to perform a rinse treatment, and then spray-dried. Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 200°C to form a film.
The spectrum of the film obtained above in the wavelength range of 400 to 1100 nm was measured using a Shimadzu UV-1800 spectrophotometer (spectrum A). This film was immersed in N-methylpyrrolidone for 30 minutes, washed with ion-exchanged water, air-dried, and the spectrum was measured again (spectrum B). The change in absorbance ΔAbs at each wavelength was calculated from the absolute value of the difference between spectrum A and spectrum B, and the maximum value of ΔAbs in the wavelength range of 400 to 1100 nm (ΔAbs_max) was used as an index for evaluating the solvent resistance. The closer the value of ΔAbs_max is to 0, the better the solvent resistance is.
-Evaluation criteria-
A: ΔAbs_max is less than 0.1 B: ΔAbs_max is 0.1 or more and less than 0.2 C: ΔAbs_max is 0.2 or more and less than 0.3 D: ΔAbs_max is 0.3 or more

<Evaluation of rectangularity>
A composition for forming an undercoat layer (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 at 220° C. for 300 seconds using a hot plate to form an undercoat layer, thereby obtaining a silicon wafer (support) with an undercoat layer. Next, each photocurable composition was applied by spin coating so that the film thickness after post-baking would be 0.5 μm. Next, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, the obtained composition layer was exposed to light (KrF line) with a wavelength of 248 nm through a mask having a 0.5 μm square pattern using a KrF scanner exposure machine, at an illuminance of 35,000 W/m ² and an exposure dose of 200 mJ/cm ² . Next, the silicon wafer on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and paddle development was performed for 60 seconds at 23°C using a 60% diluted solution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) to form a pattern on the silicon wafer. The silicon wafer on which the pattern was formed was fixed to the horizontal rotating table by a vacuum chuck method, and while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device, pure water was supplied from a spray nozzle in the form of a shower from above the center of rotation to perform a rinse treatment, and then spray-dried. Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 200°C to form a pattern (pixel).
A cross section of the produced pixel was observed with a scanning electron microscope, the angle of the pixel sidewall with respect to the silicon wafer surface was measured, and the rectangularity was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: The angle of the pixel sidewall is 80° or more and less than 100°. B: The angle of the pixel sidewall is 75° or more and less than 80°, or 100° or more and less than 105°. C: The angle of the pixel sidewall is 70° or more and less than 75°, or 105° or more and less than 110°. D: The angle of the pixel sidewall is less than 70°, or 110° or more.

The results of each evaluation are shown in the following table. In addition, in the following table, the content of the specific compound in the total solid content of the photocurable composition is shown in the column "Content of specific compound."

As shown in the table above, the examples had better adhesion and solvent resistance evaluation results than the comparative examples.

When the exposure light source for the photocurable compositions used in Examples 1 to 30 was changed from KrF rays to i-rays (wavelength 365 nm) and similar evaluations were performed on the adhesion, solvent resistance, and rectangularity, the results were equivalent to those obtained with KrF exposure.

Claims (11)

A photocurable composition comprising at least one compound A selected from the compounds represented by any one of formulas (A-1) to (A-6), a resin, and a photopolymerization initiator,
a photocurable composition, the content of the compound A being 0.005 to 2 mass% based on the total solid content of the photocurable composition;
In the formula, R ^a1 to R ^a13 each independently represent a hydrogen atom or a methyl group. The photocurable composition according to claim 1, wherein the compound A is at least one selected from the group consisting of a compound represented by formula (A1-01), a compound represented by formula (A1-02), a compound represented by formula (A5-01), and a compound represented by formula (A5-02).
The photocurable composition according to claim 1 or 2 further comprises a compound having a structure different from that of compound A, which is a trifunctional to hexafunctional polymerizable compound having 3 to 6 ethylenically unsaturated bond-containing groups. The photocurable composition according to claim 1 or 2, wherein the resin includes a resin having an ethylenically unsaturated bond-containing group. The photocurable composition according to claim 4, wherein the resin having an ethylenically unsaturated bond-containing group contains a group represented by any one of formulas (b-1) to (b-3).
In formula (b-1), * represents a bond, R ^b1 represents a hydrogen atom or a methyl group, and R ^b2 represents a hydrogen atom or an organic group;
In formula (b-2), * represents a bond, and R ^b3 represents a hydrogen atom or a methyl group;
In formula (b-3), * represents a bond, R ^b4 represents a hydrogen atom or a methyl group, and R ^b5 represents a hydrogen atom or an organic group. The photocurable composition according to claim 1 or 2, further comprising a coloring material. The photocurable composition according to claim 1 or 2, further comprising a compound having a quaternary ammonium cation. A film obtained using the photocurable composition according to claim 1 or 2. An optical filter having the film according to claim 8. A solid-state imaging device having the film according to claim 8. An image display device having the film according to claim 8.