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

Abstract

This invention provides a photocurable composition comprising at least one compound A selected from formulas (A-1) to (A-6), a resin, and a photopolymerization initiator, wherein the content of compound A in the total solids component of the photocurable composition is 0.005 to 2% by mass. This invention also provides a film, filter, solid-state imaging element, and image display device made using the aforementioned photocurable composition.

Description

TECHNICAL FIELD

[0001] The present application relates to a photocurable composition. Further, the present application relates to a film, an optical filter, a solid-state imaging device, and an image display device using the photocurable composition. BACKGROUND

[0002] A solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) is used in a video camera, a digital camera, a mobile phone with a camera function, and the like. Further, in the solid-state imaging device, an optical filter such as a color filter is provided. The optical filter is manufactured using, for example, a photocurable composition containing a polymerizable compound and a photopolymerization initiator (see Patent Literature 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent Application Laid-Open No. 2020-181041

[0006] In recent years, the miniaturization of the pattern size of the optical filter used in a solid-state imaging device and the like is being pursued. However, as the pattern size becomes smaller, the adhesion to the support tends to be insufficient.

[0007] Further, with respect to the film obtained using the photocurable composition, further improvement in the solvent resistance is required.

[0008] The present inventors have studied the composition described in Patent Literature 1, and as a result, found that there is room for further improvement in the solvent resistance and the adhesion to the support of the film obtained. SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] Therefore, an object of the present application is to provide a photocurable composition capable of forming a film excellent in adhesion and solvent resistance. Further, an object of the present application is to provide a film, an optical filter, a solid-state imaging device, and an image display device.

[0011] MEANS FOR SOLVING THE PROBLEMS

[0012] According to the study by the present inventors, it has been found that the above objects can be achieved by the photocurable composition described below, and thus the present application has been accomplished. Therefore, the present application provides the following.

[0013] <1> A photocurable composition containing a compound A selected from at least one of the compounds represented by any one of Formula (A-1) to Formula (A-6), a resin, and a photopolymerization initiator,

[0014] The content of the above-mentioned compound A in the total solid components of the above-mentioned photocurable composition is 0.005 to 2 mass %,

[0015] [Chemical Formula 1]

[0016]

[0017] In the formula, R a1 ~R a13 each independently represent a hydrogen atom or a methyl group.

[0018] <2> The photocurable composition according to <1>, wherein the above-mentioned compound A is at least one selected from the group consisting of a compound represented by formula (Al-01), a compound represented by formula (Al-02), a compound represented by formula (A5-01), and a compound represented by formula (A5-02).

[0019] [Chemical Formula 2]

[0020]

[0021] <3> The photocurable composition according to <1> or <2>, further comprising a 3 to 6 functional polymerizable compound having a structure different from the above-mentioned compound A and having 3 to 6 groups containing an ethylenic unsaturated bond.

[0022] <4> The photocurable composition according to any one of <1> to <3>, wherein the above-mentioned resin includes a resin having a group containing an ethylenic unsaturated bond.

[0023] <5> The photocurable composition according to <4>, wherein the above-mentioned resin having a group containing an ethylenic unsaturated bond contains a group represented by any one of formula (b-1) to formula (b-3),

[0024] [Chemical Formula 3]

[0025]

[0026] In formula (b-1), * represents a binding bond, R b1 represents a hydrogen atom or a methyl group, R b2 represents a hydrogen atom or an organic group,

[0027] In formula (b-2), * represents a binding bond, R b3 represents a hydrogen atom or a methyl group,

[0028] In formula (b-3), * represents a binding bond, R b4 represents a hydrogen atom or a methyl group, R b5 represents a hydrogen atom or an organic group.

[0029] <6> The photocurable composition according to any one of <1> to <5> further contains a colorant.

[0030] <7> The photocurable composition according to any one of <1> to <6> further contains a compound having a quaternary ammonium cation.

[0031] <8> A film obtained using any one of <1> to <7> of a photocurable composition.

[0032] <9> A filter having the membrane described in <8>.

[0033] <10> A solid-state imaging element having the film described in <8>.

[0034] <11> An image display device having the film described in <8>.

[0035] Invention Effects

[0036] According to the present invention, a photocurable composition capable of forming a film with excellent adhesion and solvent resistance can be provided. Furthermore, the present invention can provide a film, a filter, a solid-state imaging element, and an image display device. Detailed Implementation

[0037] The present invention will now be described in detail.

[0038] In this specification, “~” is used to imply that the values ​​recorded before and after it are the lower and upper limits.

[0039] In the designation of groups (atomic groups) in this specification, the designations without substitution and without substitution include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl).

[0040] In this specification, the term "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Furthermore, examples of light used in 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, electron beams, and other photochemical rays or radiation.

[0041] In this specification, “(meth)acrylate” means either or both of acrylate and methacrylate, “(meth)acrylic acid” means either or both of acrylic acid and methacrylic acid, and “(meth)acryloyl” means either or both of acryloyl and methacryloyl.

[0042] In this specification, in the structural formula, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0043] In this specification, the weight-average molecular weight and number-average molecular weight are polystyrene conversion values ​​determined by GPC (gel permeation chromatography).

[0044] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition.

[0045] In this specification, pigment refers to a color material that is not easily soluble in solvents.

[0046] In this specification, the term "process" includes not only independent processes, but also processes that are not clearly distinguishable from other processes, as long as they achieve the desired effect.

[0047] <Photocurable Compositions>

[0048] The photocurable composition of the present invention is characterized in that,

[0049] It contains compound A, a resin, and a photopolymerization initiator, all of which are compounds selected from any of formulas (A-1) to (A-6).

[0050] The content of compound A in the total solids of the above-mentioned photocurable composition is 0.005 to 2% by mass.

[0051] By using the photocurable composition of the present invention, a film with excellent adhesion and solvent resistance can be formed. The reason for this effect is presumably due to the following factors.

[0052] It is speculated that compound A contains two or three (meth)acryloyl groups per molecule, and also contains OH or NH groups. Therefore, through the OH or NH groups present in these compounds, although they are free radical polymerizable compounds, they also act as chain transfer agents. Therefore, it is speculated that the free radical polymerizability of the photocurable composition during exposure can be further improved. Furthermore, it is speculated that the OH or NH groups present in compound A can also act as hydrogen bond donors, thereby, it is speculated that pseudo-crosslinks can also be formed in the film. Moreover, it is speculated that by having compound A content of 0.005 to 2% by mass in the total solids composition of the photocurable composition, the above effects are achieved evenly. Therefore, it is speculated that exposure can firmly cure to the bottom of the film, and the obtained film can have good solvent resistance or adhesion to the support.

[0053] Furthermore, when pixels are formed by using the photocurable composition of the present invention and forming patterns by photolithography, pixels with excellent rectangularity can be formed. Therefore, the photocurable composition of the present invention can be preferably used for pattern formation in photolithography.

[0054] The photocurable composition of the present invention is preferably used as a photocurable composition for filters. Examples of filters include color filters, infrared transmission filters, and infrared cutoff filters, with color filters being preferred.

[0055] Furthermore, when using a photocurable composition containing a colorant, as the colorant content in the total solids of the photocurable composition increases, the amount of materials other than the colorant decreases relatively. Therefore, for photocurable compositions with high colorant concentrations, the adhesion between the obtained film and the support and the solvent resistance tend to be low. Consequently, the rectangularity of the obtained pixels also tends to decrease more easily. However, the photocurable composition of the present invention can form a film with excellent adhesion and solvent resistance even when the colorant content in the total solids of the photocurable composition is increased. Furthermore, it can also form pixels with excellent rectangularity. Therefore, the photocurable composition of the present invention exhibits particularly significant effects when applied to photocurable compositions with high colorant concentrations (for example, photocurable compositions with a colorant content of 35% by mass or more, preferably 40% by mass or more, and more preferably 45% by mass or more in the total solids of the photocurable composition).

[0056] As a color filter, a filter having colored pixels that allow light of a specific wavelength to pass through can be cited as an example. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of the color filter can be formed using a photocurable composition containing colored pigments.

[0057] The maximum absorption wavelength of the infrared cutoff filter is preferably located in the wavelength range of 700–1800 nm, more preferably in the wavelength range of 700–1300 nm, and even more preferably in the wavelength range of 700–1000 nm. Furthermore, the transmittance of the infrared cutoff filter in all wavelength ranges from 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Furthermore, the transmittance at at least one location within the wavelength range of 700–1800 nm is preferably 20% or less. Furthermore, the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at 550 nm (absorbance Amax / absorbance A550) is preferably 20–500, more preferably 50–500, even more preferably 70–450, and particularly preferably 100–400. The infrared cutoff filter can be formed using a photocurable composition containing an infrared absorbing colorant.

[0058] An infrared transmission filter is a filter that allows at least a portion of infrared light to be transmitted. Preferably, an infrared transmission filter is a filter that blocks at least a portion of visible light while allowing at least a portion of infrared light to be transmitted. As an infrared transmission filter, a filter that satisfies the following spectral characteristics is preferred: a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400–640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100–1300 nm. An infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).

[0059] (1): A filter with 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.

[0060] (2): A filter with 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.

[0061] (3): A filter with 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.

[0062] (4): A filter with 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.

[0063] (5): A filter with 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.

[0064] The concentration of solid components in the photocurable composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0065] The components used in the photocurable composition of the present invention will be described below.

[0066] <<Specific Compound (Compound A)>>

[0067] The photocurable composition of the present invention contains at least one compound A selected from any of formulas (A-1) to (A-6). Hereinafter, compounds represented by any of formulas (A-1) to (A-6) will also be referred to as specific compounds.

[0068] [Chemical Formula 4]

[0069]

[0070] In the formula, R a1 ~R a13 Each can be used to represent a hydrogen atom or a methyl group independently.

[0071] As specific examples of a particular compound, the following compounds can be cited.

[0072] [Chemical Formula 5]

[0073]

[0074] [Chemical Formula 6]

[0075]

[0076] The specific compound is preferably selected from at least one of the following: 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). According to this method, the adhesion or solvent resistance of the obtained membrane can be further improved.

[0077] The content of the specific compound in the total solids component of the photocurable composition is 0.005 to 2% by mass. The upper limit is preferably 1.5% by mass or less, more preferably 1% by mass or less. The lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0078] The photocurable composition of the present invention may contain only one specific compound or two or more specific compounds. When it contains two or more specific compounds, their total amount is within the above-mentioned range.

[0079] <<Other Polymer Compounds>>

[0080] The photocurable composition of the present invention preferably further contains a 3-6 functional polymeric compound (hereinafter also referred to as other polymeric compounds) having a structure different from the specific compounds described above and having 3-6 groups containing olefinic unsaturated bonds. Examples of olefinic unsaturated groups in other polymeric compounds include vinyl, (meth)allyl, and (meth)acryloyl groups. Other polymeric compounds are preferably free radical polymeric compounds.

[0081] Other polymerizable compounds are preferably monomers. The molecular weight of these other polymerizable compounds is preferably between 100 and 2500. The upper limit is preferably below 2000, more preferably below 1500. The lower limit is preferably above 150, more preferably above 250.

[0082] From the viewpoint of the storage stability of photocurable compositions, the number of groups containing olefinic unsaturated bonds (hereinafter referred to as C=C value) in other polymeric compounds is preferably 2 to 14 mmol / g. 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 a polymeric compound is calculated by dividing the number of groups containing olefinic unsaturated bonds contained in one molecule of the polymeric compound by the molecular weight of the polymeric compound.

[0083] As a specific example of other polymerizable compounds, the compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215 can be cited.

[0084] In addition, as a specific example of other polymeric compounds, the compound described in Taiwan Patent Application Publication No. 201832008 can also be cited.

[0085] Other polymerizable compounds are preferably dipentaerythritol tri(meth)acrylate (commercially available, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; SHIN-NAKAMURA CHEMICAL Co., Ltd.), and compounds with these (meth)acryloyl groups bonded via ethylene glycol and / or propylene glycol residues (e.g., SR454, SR499 commercially available from SARTOMER Company, Inc.). Furthermore, as other polymerizable compounds, diglyceride EO (ethylene oxide) can also be used to modify (meth)acrylates (as a commercially available product, 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 TOAGOSEICO.,LTD.), NK Oligo UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co.,Ltd.), and DPHA-40H (manufactured by Nippon Kayaku Co.,Ltd.). (manufactured by KYOEISHA CHEMICAL CO.,LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by KYOEISHA CHEMICAL CO.,LTD.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co.,Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL CO.,LTD.), ARONIX MT-3041, 3042 (manufactured by TOAGOSEI CO.,LTD., polymeric compounds containing amines), ARONIX M-510, 520 (manufactured by TOAGOSEI CO.,LTD.).Etercure 6361-100 (manufactured by Eternal Materials Co., Ltd., a polymeric compound with an acidic group), EECRYL 80 (a tetrafunctional monomer containing an amine, manufactured by DAICEL-ALLNEX LTD.), EECRYL 7100 (a difunctional monomer containing an amine, manufactured by DAICEL-ALLNEX LTD.), CN371NS (a difunctional monomer containing an amine, manufactured by Arkema SA), 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.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid: manufactured by KYOEISHA CHEMICAL CO.,LTD.). Polymer compounds having dendritic or hyperbranched structures, as described in Japanese Patent Application Publication No. 2023-043479, and polymer compounds described in Japanese Patent Application Publication No. 2023-529984, etc.

[0086] The content of other polymeric compounds in the total solids component 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, more preferably 5% by mass or more.

[0087] The photocurable composition preferably contains 0.05 to 20 parts by weight of the specific compound described above, relative to 100 parts by weight of other polymerizable compounds. The upper limit is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. The lower limit is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more.

[0088] The photocurable composition of the present invention may contain only one other polymeric compound, or it may contain two or more other polymeric compounds. When it contains two or more polymeric compounds, their total amount is preferably within the above-mentioned range.

[0089] <<Resin>>

[0090] The photocurable composition of the present invention contains a resin. The resin is formulated, for example, for dispersing pigments or the like in the photocurable composition, or for use as an adhesive. Additionally, the resin primarily used for dispersing pigments or the like in the photocurable composition is also referred to as a dispersant. However, this use of the resin is one example; it can also be used for purposes other than this.

[0091] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably below 1,000,000, more preferably below 500,000. The lower limit is preferably above 4,000, more preferably above 5,000.

[0092] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyaryl ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Furthermore, as a resin, the resins described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, the end-capped polyisocyanate resins described in Japanese Patent Application Publication No. 2016-222891, the resins described in Japanese Patent Application Publication No. 2020-122052, the resins described in Japanese Patent Application Publication No. 2020-111656, the resins described in Japanese Patent Application Publication No. 2020-139021, the resins described in Japanese Patent Application Publication No. 2017-138503 containing structural units having a ring structure in the main chain and biphenyl structural units in the side chain, the resins described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, and the alkali-soluble resins described in Japanese Patent Application Publication No. 2020-186325 can also be used. The resin represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0078339, the copolymer containing epoxy groups and acid groups as described in International Patent Publication No. 2022 / 030445, the resin described in Japanese Patent Application Publication No. 2018-135514, the copolymer described in Japanese Patent Application Publication No. 2020-041046, the resin described in Japanese Patent Application Publication No. 2023-033156, the resin described in Japanese Patent Application Publication No. 2023-030386, the resin described in Japanese Patent Application Publication No. 2023-027753, the resin described in Japanese Patent Application Publication No. 2020-139021, the resin described in Japanese Patent Application Publication No. 2023-074038, and the resin described in Japanese Patent Application Publication No. 2023-079666.

[0093] (Specific resin)

[0094] The photocurable composition of the present invention preferably contains a resin having a group containing an olefinic unsaturated bond (hereinafter also referred to as a specific resin).

[0095] Examples of olefinically unsaturated groups found in specific resins include vinyl, (meth)allyl, and (meth)acryloyl groups.

[0096] The weight-average molecular weight of the specific resin is preferably between 2,000 and 50,000. The upper limit is preferably below 40,000, more preferably below 30,000. The lower limit is preferably above 3,000, more preferably above 5,000.

[0097] The value of the group containing olefinic unsaturated bonds (hereinafter also referred to as the C=C value) of a 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 a specific resin is a numerical value representing the molar amount of the group containing olefinic unsaturated bonds per 1g of the solid component 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. And when it cannot be calculated from the structural formula but can be calculated from the raw materials used in the synthesis of the specific resin, the value calculated from the loaded raw materials is used. Furthermore, regarding the value of the group containing olefinic unsaturated bonds of the specific resin, when it cannot be calculated from the raw materials used in the synthesis of the specific resin, the value determined by hydrolysis is used. Specifically, the component (a) containing the group containing olefinic unsaturated bonds is extracted from the specific resin by alkali treatment, and the content is determined by high performance liquid chromatography (HPLC) and calculated by the following formula. Furthermore, when the above-mentioned component (a) cannot be extracted from a specific resin by alkali treatment, the value determined by NMR (nuclear magnetic resonance) is used.

[0098] The number of olefinically unsaturated groups in a specific resin [mmol / g] = (content of component (a) [ppm] / molecular weight of component (a) [g / mol]) / (weighing value of specific resin [g] × (concentration of solid components of specific resin [mass%] / 100) × 10)

[0099] The specific resin preferably contains groups represented by any of formulas (b-1) to (b-3), and more preferably contains groups represented by formula (b-1) or formula (b-3). According to this method, it is possible to form a film with better adhesion to the support and better solvent resistance.

[0100] [Chemical Formula 7]

[0101]

[0102] In equation (b-1), * represents a bonding bond, R b1 R represents a hydrogen atom or a methyl group. b2 Indicates a hydrogen atom or an organic group.

[0103] In equation (b-2), * represents a bonding bond, R b3 Indicates a hydrogen atom or a methyl group.

[0104] In equation (b-3), * represents a bonding bond, R b4 R represents a hydrogen atom or a methyl group. b5 It represents a hydrogen atom or an organic group.

[0105] R as in equation (b-1) b2 and R in equation (b-3) b5 Examples of organic groups represented include alkyl, aryl, and heteroaryl groups.

[0106] The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include alkoxy, aryloxy, and -NR. A111 R A112 -SO2NR A113 R A114 -COOR A115 -CONR A116 R A117 etc. R A111 ~R A117 Each can be represented independently as either alkyl or aryl.

[0107] The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, nitro groups, cyano groups, alkoxy groups, aryloxy groups, and -NR groups. A111 R A112 -SO2NR A113 R A114 -COOR A115 -CONR A116 R A117 etc. R A111 ~R A117 Each can be represented independently as either alkyl or aryl.

[0108] The heteroaryl group is preferably a 5-membered or 6-membered ring heteroaryl group. The heteroatoms in the heteroaryl group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have substituents. Examples of substituents include halogen atoms, nitro groups, cyano groups, alkoxy groups, aryloxy groups, and -NR groups. A111 R A112 -SO2NR A113 R A114 -COOR A115 -CONR A116 R A117 etc. R A111 ~R A117 Each can be represented independently as either alkyl or aryl.

[0109] R in equation (b-1) b2 and R in equation (b-3) b5 Hydrogen atoms are preferred.

[0110] The specific resin is preferably a resin containing repeating units, which have groups containing olefinic unsaturated bonds on their side chains. The repeating units having groups containing olefinic unsaturated bonds on their side chains are preferably repeating units represented by formula (B1-1).

[0111] [Chemical Formula 8]

[0112]

[0113] In the formula, Y b11 L represents a trivalent linker group. b11 Indicates a single bond or a divalent linker, A b11 This indicates a group containing an alkene unsaturated bond.

[0114] As Y b11 Examples of trivalent linking groups include poly(meth)acrylic acid linking groups, polyalkylimide linking groups, polyester linking groups, polyurethane linking groups, polyurea linking groups, polyamide linking groups, polyether linking groups, and polystyrene linking groups, with poly(meth)acrylic acid linking groups or polyalkylimide linking groups being more preferred.

[0115] As L b11 Examples of divalent linking groups include alkylene (preferably alkylene with 1 to 12 carbon atoms), arylene (preferably arylene with 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups.

[0116] A b11 This indicates a group containing an alkene unsaturated bond. As a group containing an alkene unsaturated bond,

[0117] Examples of suitable groups include vinyl, (meth)allyl, (meth)acryloyl, and groups represented by any of the above formulas (b-1) to (b-3), preferably groups represented by any of the above formulas (b-1) to (b-3), and more preferably groups containing a group represented by formula (b-1) or a group represented by formula (b-3).

[0118] The content of the repeating unit represented by formula (B1-1) is preferably 1 mol% or more, more preferably 1 to 80 mol% of all repeating units in the specific resin. 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.

[0119] Certain resins may contain repeating units with acid groups. Examples of acid groups include carboxyl, sulfonyl, and phosphate groups.

[0120] When a particular resin contains repeating units with acid groups, the content of repeating units with acid groups in the particular resin is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol% of all repeating units in the particular resin.

[0121] When a particular resin contains repeating units with acid groups, the acid value of the particular resin is preferably 5 to 200 mg KOH / g. The upper limit is preferably 150 mg KOH / g or less, more preferably 100 mg KOH / g or less, and even more preferably 80 mg KOH / g or less. The lower limit is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and even more preferably 20 mg KOH / g or more.

[0122] Certain resins may contain repeating units with grafted chains. Furthermore, in this specification, a grafted chain refers to a polymer chain that branches off from the main chain of the repeating unit. As a grafted chain, the number of atoms after removing hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500.

[0123] The grafted chain preferably contains repeating units with at least one structure selected from the group consisting of polyester, polyether, poly(meth)acrylic acid, polystyrene, polyurethane, polyurea, and polyamide structures; more preferably, it contains repeating units with at least one structure selected from the group consisting of polyester, polyether, poly(meth)acrylic acid, and polystyrene structures; even more preferably, it contains repeating units with at least one structure selected from the group consisting of polyester, polyether, and poly(meth)acrylic acid structures; even more preferably, it contains repeating units with polyester or polyether structures; and particularly preferably, it contains repeating units with polyester structures.

[0124] Examples of repeating units in a polyester structure include those represented by formulas (G-1), (G-4), or (G-5). Examples of repeating units in a polyether structure include those represented by formula (G-2). Examples of repeating units in a poly(meth)acrylic acid structure include those represented by formula (G-3). Examples of repeating units in a polystyrene structure include those represented by formula (G-6).

[0125] [Chemical Formula 9]

[0126]

[0127] In the above formula, R G1 and R G2 Each can be used independently to represent an alkylene group.

[0128] R G1 The alkylene group represented preferably has 1 to 20 carbon atoms, more preferably 2 to 16, and even more preferably 2 to 12. The alkylene group is preferably straight-chain or branched, more preferably straight-chain.

[0129] R G2 The alkylene group represented preferably has 1 to 10 carbon atoms, more preferably 1 to 5, further preferably 2 to 5, and even more preferably 2 or 3. The alkylene group is preferably straight-chain or branched, more preferably straight-chain.

[0130] In the above formula, R G3 Q represents a hydrogen atom or a methyl group. G1 Indicates -O- or -NH-, L G1 R represents a single bond or a divalent linker. G4 It represents a hydrogen atom or a substituent.

[0131] As L G1 Examples of divalent linking groups include alkylene (preferably alkylene with 1 to 12 carbon atoms), alkeneoxy (preferably alkeneoxy with 1 to 12 carbon atoms), oxoalkylene carbonyl (preferably oxoalkylene carbonyl with 1 to 12 carbon atoms), aryl (preferably aryl with 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.

[0132] As R G4 Examples of substituents include hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic, alkyl thioether, aryl thioether, and heterocyclic thioether.

[0133] R G5R represents a hydrogen atom or a methyl group. G6 Indicates aryl. R G6 The aryl group represented preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. G6 The aryl group may have substituents. Examples of substituents include hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic, alkyl thioether, aryl thioether, and heterocyclic thioether.

[0134] The terminal structure of the grafted chain is not particularly limited. It can be a hydrogen atom or a substituent. Examples of substituents include hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic, alkyl thioether, aryl thioether, and heterocyclic thioether groups. Among these, groups with steric repulsion are preferred, and alkyl or alkoxy groups with 5 to 24 carbon atoms are preferred. Alkyl and alkoxy groups can be linear, branched, or cyclic, with linear or branched groups being preferred.

[0135] As a grafting chain, the preferred structure is represented by formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a), and more preferably, it is represented by formula (G-1a), formula (G-4a) or formula (G-5a).

[0136] [Chemical Formula 10]

[0137]

[0138] In the above formula, R G1 and R G2 R represents alkylene groups respectively. G3 Q represents a hydrogen atom or a methyl group. G1 Indicates -O- or -NH-, L G1 R represents a single bond or a divalent linker. G4 R represents a hydrogen atom or substituent. G5 R represents a hydrogen atom or a methyl group. G6 Indicates aryl, W 100 Represents a hydrogen atom or substituent, where n1 to n6 independently represent integers greater than 2. Regarding R... G1 ~R G6 Q G1 L G1 R as described in equations (G-1) to (G-6) G1 ~R G6 Q G1 L G1 The meanings are the same, and the preferred ranges are also the same.

[0139] In equations (G-1a) to (G-6a), W100 Substituents are preferred. Examples of substituents include hydroxyl, carboxyl, alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic, alkyl thioether, aryl thioether, and heterocyclic thioether groups. Among these, groups with steric repulsion are preferred, and alkyl or alkoxy groups with 5 to 24 carbon atoms are preferred. Alkyl and alkoxy groups can be linear, branched, or cyclic, with linear or branched groups being preferred.

[0140] In formulas (G-1a) to (G-6a), n1 to n6 are preferably integers from 2 to 100, more preferably integers from 2 to 80, and even more preferably integers from 8 to 60.

[0141] In equation (G-1a), R in each repeating unit when n1 is 2 or more G1 They can be the same or different. And, when R... G1 When there are two or more different repeating units, the arrangement of each repeating unit is not particularly limited and can be random, alternating, or block-like. The same applies in formulas (G-2a) to (G-6a). Furthermore, it is preferred that the graft chain is a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R... G1 It is a structure containing two or more different repeating units.

[0142] The weight-average molecular weight of the repeating unit with grafted chains is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500. Furthermore, in this specification, the weight-average molecular weight of the repeating unit with grafted chains is a value calculated based on the weight-average molecular weight of the raw material monomers used in the polymerization of the repeating unit. For example, the repeating unit with grafted chains can be formed by polymerizing a macromonomer. Here, a macromonomer refers to a polymeric compound with polymerizable groups introduced at the polymer terminus. When using a macromonomer to form the repeating unit with grafted chains, the weight-average molecular weight of the macromonomer corresponds to the repeating unit with grafted chains.

[0143] When a particular resin contains repeating units with grafted chains, the content of repeating units with grafted chains is preferably 1 to 60 mol% of all repeating units in the particular resin. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.

[0144] It is also preferred that a particular resin contains repeating units derived from monomeric components containing compounds represented by formula (ED1) and / or compounds represented by formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimers").

[0145] [Chemical Formula 11]

[0146]

[0147] In equation (ED1), R 1 and R 2 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms that may have substituents.

[0148] [Chemical Formula 12]

[0149]

[0150] In formula (ED2), R represents an organic group with 1 to 30 hydrogen atoms or carbon atoms. For details regarding formula (ED2), please refer to Japanese Patent Application Publication No. 2010-168539, which is incorporated herein by reference.

[0151] For specific examples of ether dimers, please refer to paragraph 0317 of Japanese Patent Application Publication No. 2013-029760, which is incorporated herein by reference.

[0152] The specific resin also preferably contains repeating units derived from compounds represented by the following formula (X).

[0153] [Chemical Formula 13]

[0154]

[0155] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group with 2 to 10 carbon atoms, and R3 represents a hydrogen atom or an alkyl group with 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer from 1 to 15.

[0156] The specific resin is also preferably a resin containing repeating units represented by formula (Ac-2).

[0157] [Chemical Formula 14]

[0158]

[0159] In equation (Ac-2), Ar 10 L represents a group containing an aromatic carboxyl group. 11 Indicates -COO- or -CONH-, L 12 P represents a trivalent linker group. 10 This refers to a polymer chain containing repeating units (with groups containing olefinic unsaturated bonds on the side chains).

[0160] Ar as in equation (Ac-2) 10Examples of aromatic carboxyl groups include structures derived from aromatic tricarboxylic anhydrides and structures derived from aromatic tetracarboxylic anhydrides. Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds with the following structures.

[0161] [Chemical Formula 15]

[0162]

[0163] In the above formula, Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0164] [Chemical Formula 16]

[0165]

[0166] Ar 10 The groups representing aromatic carboxyl groups can also have groups containing olefinic unsaturated bonds. As Ar 10 Specific examples of groups containing aromatic carboxyl groups may include those represented by formula (Ar-11), formula (Ar-12), formula (Ar-13), etc.

[0167] [Chemical Formula 17]

[0168]

[0169] In formula (Ar-11), n1 represents an integer from 1 to 4, preferably 1 or 2, and more preferably 2.

[0170] In formula (Ar-12), n2 represents an integer from 1 to 8, preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 2.

[0171] In formula (Ar-13), n3 and n4 independently represent integers from 0 to 4, preferably integers from 0 to 2, more preferably 1 or 2, and even more preferably 1. At least one of n3 and n4 is an integer greater than or equal to 1.

[0172] In equation (Ar-13), Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2).

[0173] In equations (Ar-11) to (Ar-13), *1 indicates that it is related to L. 10 The bonding positions.

[0174] L in equation (Ac-2) 11 It can be represented as -COO- or -CONH-, preferably -COO-.

[0175] L as in equation (Ac-2) 12 The trivalent linking group can include alkyl groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combinations of two or more of these. Examples of alkyl groups include aliphatic alkyl groups and aromatic alkyl groups. The aliphatic alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic alkyl group can be straight-chain, branched, or cyclic. The aromatic alkyl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. The alkyl group can have substituents. Examples of substituents include hydroxyl groups. 12 The trivalent linking group represented is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

[0176] [Chemical Formula 18]

[0177]

[0178] In equation (L12-1), L 12b X represents a trivalent linker group. 1 S represents S, and *1 represents L in equation (Ac-2). 11 The bonding position, *2 indicates the P in equation (Ac-2). 10 The bonding position. As L 12b Examples of trivalent linking groups include hydrocarbon groups; groups composed of a combination of hydrocarbon groups and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-, preferably hydrocarbon groups or groups composed of a combination of hydrocarbon groups and -O-.

[0179] In equation (L12-2), L 12c X represents a trivalent linker group. 1 S represents S, and *1 represents L in equation (Ac-2). 11 The bonding position, *2 indicates the P in equation (Ac-2). 10 The bonding position. As L 12c The trivalent linking group represented can be a hydrocarbon group; a combination of hydrocarbon groups and a group formed by at least one of -O-, -CO-, -COO-, -OCO-, -NH- and -S-, preferably a hydrocarbon group.

[0180] P in equation (Ac-2) 10This refers to a polymer chain containing repeating units (with groups containing olefinic unsaturated bonds on the side chains).

[0181] P 10 The polymer chain represented is preferably a polymer chain containing repeating units having groups represented by any of the formulas (b-1) to (b-3) above on the side chains, and more preferably a polymer chain containing repeating units having groups represented by formula (b-1) or formula (b-3) on the side chains.

[0182] As P 10 The polymer chain referred to may be a polymer chain containing repeating units of at least one structure selected from the group consisting of polyester, polyether, poly(meth)acrylic acid, polystyrene, polyurethane, polyurea, and polyamide structures. As a repeating unit of the polyester structure, repeating units of the structure represented by formula (G-1), (G-4), or (G-5) above can be cited. As a repeating unit of the polyether structure, repeating units of the structure represented by formula (G-2) above can be cited. As a repeating unit of the poly(meth)acrylic acid structure, repeating units of the structure represented by formula (G-3) above can be cited. As a repeating unit of the polystyrene structure, repeating units of the structure represented by formula (G-6) above can be cited.

[0183] As P 10 The repeating units of the polymer chain represented, which have olefinically unsaturated groups on their side chains, can be exemplified by the repeating units represented by the above formula (B1-1). This constitutes P 10 The proportion of repeating units having olefinically unsaturated groups on their side chains 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.

[0184] P 10 The polymer chain represented preferably has repeating units containing acid groups. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups. When P 10 When the polymer chain represented contains repeating units with acid groups, it constitutes P. 10 The proportion of repeating units with acid groups in all repeating units is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%.

[0185] P 10The weight-average molecular weight of the polymer chain represented 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.

[0186] Certain resins can be used as adhesives or dispersants.

[0187] (Other resins)

[0188] The photocurable composition of the present invention can also be further used with resins other than the specific resins described above (hereinafter also referred to as other resins).

[0189] As other resins, resins having acid groups are preferred. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, phenolic hydroxyl groups, etc.

[0190] The acid value of the resin containing acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, more preferably 50 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 300 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. The weight-average molecular weight (Mw) of the resin containing acid groups is preferably 5000 to 100000, more preferably 5000 to 50000. The number-average molecular weight (Mn) of the resin containing acid groups is preferably 1000 to 20000.

[0191] The resin containing acid groups preferably contains repeating units with acid groups on their side chains, and more preferably contains 5 to 70 mol% of repeating units with acid groups on their side chains in all repeating units of the resin. The upper limit of the content of repeating units with acid groups on their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units with acid groups on their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.

[0192] Regarding resins containing acid groups, for example, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins containing acid groups can also be used. Moreover, there are no particular limitations on the method for introducing acid groups into the resin; for example, the method described in Japanese Patent No. 6349629 can be cited. Additionally, as a method for introducing acid groups into the resin, a method of introducing acid groups by reacting an acid anhydride with a hydroxyl group generated in the ring-opening reaction of an epoxy group can also be cited.

[0193] Resins containing base groups can also be used as other resins. Resins containing base groups are preferably resins containing repeating units with base groups on their side chains, more preferably copolymers containing repeating units with and without base groups on their side chains, and even more preferably block copolymers containing repeating units with and without base groups on their side chains. Resins containing base groups can also be used as dispersants. The amine value of the resin containing base groups is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, more preferably 100 mg KOH / g or less.

[0194] Commercially available resins containing alkali 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 BYKChemie GmbH), and Solsperse. Models 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan Limited), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resins containing base groups can also include the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Application Publication No. 2018-156021, and the vinyl resins containing base groups described in paragraphs 0150 to 0153 of Japanese Patent Application Publication No. 2019-184763, all of which are incorporated herein by reference.

[0195] Other resins preferably include resins with acid groups and resins with base groups. This method can further improve the storage stability of the photosensitive composition. When resins with acid groups and resins with base groups are used together, the content of the resin with base groups is preferably 20 to 500 parts by weight relative to 100 parts by weight of the resin with acid groups, more preferably 30 to 300 parts by weight, and even more preferably 50 to 200 parts by weight.

[0196] As other resins, resins having aromatic carboxyl groups are also preferred. In resins having aromatic carboxyl groups, the aromatic carboxyl groups may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that the aromatic carboxyl groups are contained in the main chain of the repeating unit. Furthermore, in this specification, an aromatic carboxyl group refers to a group in which one or more carboxyl groups are bonded to an aromatic ring. In aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2. Examples of resins having aromatic carboxyl groups include those described in paragraphs 0082 to 0107 of International Publication No. 2021 / 166858.

[0197] As other resins, it is preferred to use at least one selected from graft polymers, star polymers, block copolymers, and resins whose polymer chains are at least one end capped with an acid group. Such resins are preferably used as dispersants.

[0198] Examples of graft polymers include resins containing repeating units with graft chains. Examples of graft chains include those containing at least one structure selected from polyester, polyether, polystyrene, and poly(meth)acrylic acid structures. The terminal structure of the graft chain is not particularly limited; it can be a hydrogen atom or a substituent. Examples of substituents include alkyl, alkoxy, and alkyl sulfide groups. From the viewpoint of improving pigment dispersibility, groups with stereorepulsive effects are preferred, and alkyl or alkoxy groups with 5 to 30 carbon atoms are preferred. Alkyl and alkoxy groups can be linear, branched, or cyclic, with linear or branched forms being preferred.

[0199] Specific examples of grafted polymers include the resins described in Japanese Patent Application Publication No. 2012-255128, paragraphs 0025-0094; Japanese Patent Application Publication No. 2009-203462, paragraphs 0022-0097; and Japanese Patent Application Publication No. 2012-255128, paragraphs 0102-0166.

[0200] As a star polymer, resins with a structure in which multiple polymer chains are bonded to the core can be cited. Specific examples of star polymers include polymers C-1 to C-31 as described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0201] As a block copolymer, a block copolymer having a polymer block containing repeating units of acid groups or bases (hereinafter also referred to as block A) and a polymer block having repeating units without acid groups or bases (hereinafter also referred to as block B) is preferred. Block copolymers can also be the block copolymers described in paragraphs 0063 to 0112 of Japanese Patent Application Publication No. 2014-219665 and the block copolymers A1 described in paragraphs 0046 to 0076 of Japanese Patent Application Publication No. 2018-156021, which are incorporated herein by reference.

[0202] Examples of resins in which at least one end of a polymer chain is capped with an acid group include resins containing a structure in which at least one end of a polymer chain selected from polyester, polyether, and poly(meth)acrylic acid structures is capped with an acid group. Examples of acid groups at the end of the capped polymer chain include carboxyl, sulfonyl, and phosphate groups.

[0203] Other resins can also be used as dispersants. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Acidic dispersants (acidic resins) refer to resins in which the amount of acid groups exceeds the amount of base groups. When the total amount of acid groups and base groups is set to 100 mol%, a resin with an acid group amount of 70 mol% or more is preferred. The acid groups in the acidic dispersant (acidic resin) are preferably carboxyl groups. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Similarly, basic dispersants (basic resins) refer to resins in which the amount of base groups exceeds the amount of acid groups. When the total amount of acid groups and base groups is set to 100 mol%, a resin with a base group amount exceeding 50 mol% is preferred. The base groups in the basic dispersant are preferably amine groups.

[0204] Dispersants are also available as commercially available products. Specific examples include the Disperbyk series (e.g., Disperbyk-111, 161, 2001, etc.) manufactured by BYK-Chemie GmbH, the SOLSPERSE series (e.g., SOLSPERSE20000, 76500, etc.) manufactured by Lubrizol Japan Ltd., the Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc., A208F (manufactured by DKS Co., Ltd.), H-3606 (manufactured by DKS Co., Ltd.), and SANDET ET (manufactured by SANYO KASEI CO.,LTD.). Furthermore, the products described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Application Publication No. 2017-194662 can also be used as dispersants.

[0205] The resin content in the total solids component of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.

[0206] Relative to 100 parts by weight of the resin, the photocurable composition preferably contains 0.01 to 2 parts by weight of the aforementioned specific compound. The upper limit is preferably 1.5 parts by weight or less, more preferably 1.2 parts by weight or less, and even more preferably 1 part by weight or less. The lower limit is preferably 0.02 parts by weight or more, more preferably 0.05 parts by weight or more.

[0207] The content of the specific resin mentioned above in the total solids component of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The content of the specific resin mentioned above in the resin contained in the photocurable composition is preferably 2 to 100% by mass, more preferably 5 to 100% by mass, and even more preferably 10 to 100% by mass.

[0208] Relative to 100 parts by weight of the specific resin described above, the photocurable composition preferably contains 0.01 to 2 parts by weight of the specific compound described above. The upper limit is preferably 1.5 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.5 parts by weight or less. The lower limit is preferably 0.02 parts by weight or more, more preferably 0.05 parts by weight or more.

[0209] The photocurable composition of the present invention may contain only one type of resin or two or more types of resin. When it contains two or more types of resin, their total amount is preferably within the range described above.

[0210] <<Photopolymerization Initiator>>

[0211] The photocurable composition of the present invention contains a photopolymerization initiator. There are no particular limitations on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitizing to light in the ultraviolet to visible regions is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0212] Examples of photopolymerization initiators include haloalkanes (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, and α-amino ketone compounds. From the viewpoint of exposure sensitivity, photopolymerization initiators are preferably trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. More preferably, they are compounds selected from oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acylphosphine compounds. Oxime compounds are even more preferred. Furthermore, as photopolymerization initiators, examples include the compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No.The peroxide-based photopolymerization initiator described in 3, 2019; the photopolymerization initiator described in International Publication No. 2018 / 221177; the photopolymerization initiator described in International Publication No. 2018 / 110179; the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864; the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030; the peroxide-based initiator described in Japanese Patent Application Publication No. 2019-167313; the oxazolyl-based aminoacetophenone initiator described in Japanese Patent Application Publication No. 2020-055992; and the photopolymerization initiator described in Japanese Patent Application Publication No. 2013-190459. The oxime-based photopolymerization initiators described herein, the polymers described in Japanese Patent Application Publication No. 2020-172619, the compounds represented by formula 1 described in International Patent Application Publication No. 2020 / 152120, the compounds described in Japanese Patent Application Publication No. 2021-181406, the photopolymerization initiators described in Japanese Patent Application Publication No. 2022-013379, the compounds represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, the fluorinated fluorene oxime ester-based photoinitiators described in Japanese Patent Application Publication No. 2021-507058, the initiators described in Chinese Patent Application Publication No. 110764367, and the Japanese Patent Application Publication No. 2021-507058. The initiator described in Japanese Patent Application Publication No. 2022-518535, the initiator described in International Publication No. 2021 / 175855, the compound described in Japanese Patent Application Publication No. 2022-078550, the compound described in Korean Patent Publication No. 10-2017-0087330, the compound described in International Publication No. 2022 / 075452, the oxime ester compound described in Chinese Patent Application Publication No. 110066225, the compound described in Korean Patent Publication No. 10-2022-0076157, and the compound having a triarylamine or N-arylcarbazole skeleton in International Publication No. 2019 / 0131 The compounds described in paragraphs 0042 to 0062 of Patent No. 12, the oxime ester-based photopolymerization initiator described in Japanese Patent No. 7219378, the photopolymerization initiator described in Korean Patent Publication No. 10-2021-0146174, the photopolymerization initiator described in International Patent Publication No. 2019 / 013112, the photopolymerization initiator described in Japanese Unexamined Patent Application Publication No. 2023-033731, the initiator described in Japanese Unexamined Patent Application Publication No. 2022-515524, the initiator described in Japanese Unexamined Patent Application Publication No. 2023-517304, and the initiator described in Chinese Patent Application Publication No. 114149517, etc.

[0213] In addition, compounds described in Taiwan Patent Application Publication No. 202200534 can also be cited as photopolymerization initiators.

[0214] Specific examples of hexaaryl biimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc.

[0215] Commercially available α-hydroxy ketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-amino ketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0216] Examples of oxime compounds include those described in paragraph 0142 of International Publication No. 2022 / 085485, those described in Japanese Patent No. 5430746, those described in Japanese Patent No. 5647738, those represented by general formula (1) or described in paragraphs 0022 to 0024 of Japanese Patent Application Publication No. 2021-173858, and those represented by general formula (1) or described in paragraphs 0117 to 0120 of Japanese Patent Application Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), etc. As commercially available products, examples 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-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 Changzhou Tronly New Electronic Materials Co., Ltd.), and AdekaOptomer N-1919 (ADEKA). The photopolymerization initiator 2, manufactured by CORPORATION and disclosed in Japanese Patent Application Publication No. 2012-014052, is used. Furthermore, as the oxime compound, a colorless compound or a compound with high transparency and resistance to discoloration is preferred. Commercially available examples include ADEKA ARKLS NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0217] As photopolymerization initiators, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring in a carbazole ring forming a naphthalene ring skeleton, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can also be used.

[0218] Compounds represented by formula (OX-1) can also be used as photopolymerization initiators.

[0219] [Chemical Formula 19]

[0220]

[0221] In equation (OX-1), X 1a It indicates that it contains at least one divalent linker selected from the group consisting of aromatic rings and heterocycles.

[0222] R 1a Represents a hydrogen atom or an acyl group.

[0223] R 2a Indicates alkyl or aryl.

[0224] R 3a and R 4a Each can be used independently to represent a hydrogen atom or an alkyl group.

[0225] Alk 1 and Alk 2 Each can be independently represented as an alkyl group.

[0226] R 3a With R 4a They can bond together to form a ring.

[0227] Alk 1 With Alk 2 They can bond together to form a ring.

[0228] n represents 0 or 1.

[0229] X as in equation (OX-1) 1a Examples of divalent linking groups include divalent aromatic cyclic groups, divalent heterocyclic groups, divalent groups that bond two or more aromatic rings via single bonds or linking groups, divalent groups that bond two or more heterocyclic rings via single bonds or linking groups, and divalent groups that bond aromatic rings and heterocyclic rings via single bonds or linking groups. Examples of linking groups for bonding aromatic rings to each other, heterocyclic groups to each other, or aromatic rings to heterocyclic rings include -CH2-, -O-, -CO-, -S-, and -NR. x - and groups formed by combining them, etc. Rx It represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group.

[0230] X in equation (OX-1) 1a Preferably, the group is represented by any one of the formulas (X-1) to (X-13), more preferably by a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and even more preferably by a group represented by formula (X-2) or formula (X-6).

[0231] [Chemical Formula 20]

[0232]

[0233] In the formula R X1 ~R X9 Each group independently represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group, with * indicating a bond.

[0234] R X1 ~R X9 The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0235] R X1 ~R X9 The alkenyl group preferably has 2 to 15 carbon atoms, more preferably 2 to 10. The alkenyl group can be straight-chain, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0236] R X1 ~R X9 The number of carbon atoms in the represented alkynyl group is preferably 2 to 15, more preferably 2 to 10. The alkynyl group can be straight-chain, branched, or cyclic. The alkynyl group can have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0237] R X1 ~R X9 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups.

[0238] R X1 ~R X9The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0239] R in equation (OX-1) 1a It represents a hydrogen atom or an acyl group, preferably an acyl group.

[0240] R 1a The acyl group represented is preferably composed of -C(O)-R 101 The group indicated by R. 101 It represents an aryl or heterocyclic group, preferably an aryl group.

[0241] R 101 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups. 101 The aryl group represented is preferably phenyl, methylphenyl, or naphthyl, more preferably methylphenyl or naphthyl.

[0242] R 101 The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0243] R in equation (OX-1) 2a The group is alkyl or aryl, and alkyl is preferred for its high reactivity in generating free radicals.

[0244] R 2a The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted. 2a The alkyl group represented is preferably an unsubstituted straight-chain or branched alkyl group, more preferably an unsubstituted straight-chain alkyl group.

[0245] R 2a The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but is preferably an unsubstituted aryl group.

[0246] R in equation (OX-1) 3a and R4a Each can be represented independently as a hydrogen atom or an alkyl group, preferably a hydrogen atom.

[0247] R 3a and R 4a The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0248] R 3a With R 4a They can bond together to form a ring. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring.

[0249] Alk of formula (OX-1) 1 and Alk 2 Alkyl groups are represented independently. The number of carbon atoms in an alkyl group is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and even more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0250] Alk 1 With Alk 2 They can bond together to form a ring, preferably a ring. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0251] In formula (OX-1), n ​​represents 0 or 1, preferably 0.

[0252] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Application Publication No. 2012-189997.

[0253] Compounds represented by formula (OX-2) can also be used as photopolymerization initiators.

[0254] [Chemical Formula 21]

[0255]

[0256] In equation (OX-2), R 1b and R 2b Each substituent is represented independently, R 3b ~R 7bEach can be used independently to represent a hydrogen atom or a substituent, Ar 1b This indicates an aromatic cyclic or heterocyclic group that can have substituents, and n represents 0 or 1.

[0257] As R 1b and R 2b Examples of substituents include alkyl and aryl groups, with alkyl groups being preferred. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl, alkenyl, ynyl, and heterocyclic groups. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl, alkenyl, ynyl, and heterocyclic groups.

[0258] As R 3b ~R 7b Examples of substituents include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl and aryl groups include the groups mentioned above.

[0259] R 3b ~R 7b Hydrogen atoms are preferred.

[0260] Ar 1b Ar indicates an aromatic cyclic or heterocyclic group that can have substituents. 1b Preferably, it is an aromatic cyclic group that can have substituents. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred. Examples of acyl groups include the aforementioned acyl groups.

[0261] Compounds represented by formula (OX-3) can also be used as photopolymerization initiators.

[0262] [Chemical Formula 22]

[0263]

[0264] In formula (OX-3), Ar 1c This indicates a (k+m+1) valence aromatic cyclic group or a (k+m+1) valence heterocyclic group.

[0265] Ar 2c This indicates a (k+2) valence aromatic cyclic group or a (k+2) valence heterocyclic group.

[0266] R 1c ~R 3c Substituents are represented independently.

[0267] L 1c Indicates a single key or CR 11c R 12c R 11c and R 12c Each can independently represent a hydrogen atom, alkyl group, or aryl group.

[0268] X 1c It can represent -CH2-, -O-, or -S-.

[0269] k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0270] As R 1c and R 2c Examples of substituents include alkyl and aryl groups, with alkyl groups being preferred. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl, alkenyl, ynyl, and heterocyclic groups. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl, alkenyl, ynyl, and heterocyclic groups.

[0271] R 2c Preferably, it is an alkyl group having a branched or cyclic structure.

[0272] As R 3c Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred. Examples of acyl groups include the aforementioned acyl groups.

[0273] L 1c Indicates a single key or CR 11c R 12c R 11c and R 12c Each can be independently represented by a hydrogen atom, alkyl group, or aryl group. R 11c and R 12c The meanings of alkyl and aryl groups in R are related to the meanings of R. 1c and R 2c The alkyl and aryl groups in this context have the same meaning. When k is 1, L 1c Single bonds are preferred.

[0274] X 1c It can be represented as -CH2-, -O-, or -S-, preferably -O- or -S-.

[0275] Ar 1cThis indicates a (k+m+1) valent aromatic cyclic group or a (k+m+1) valent heterocyclic group, preferably a (k+m+1) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0276] Ar 2c The term represents a (k+2) valent aromatic cyclic group or a (k+2) valent heterocyclic group, preferably a (k+2) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0277] k represents 0 or 1, preferably 0.

[0278] m represents an integer from 0 to 4, preferably 0 or 1, and more preferably 1.

[0279] n represents 0 or 1, preferably 0.

[0280] The following are specific examples of oxime compounds that are preferably used in this invention, but the invention is not limited to these.

[0281] [Chemical Formula 23]

[0282]

[0283] [Chemical Formula 24]

[0284]

[0285] [Chemical Formula 25]

[0286]

[0287] [Chemical Formula 26]

[0288]

[0289] [Chemical Formula 27]

[0290]

[0291] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350–500 nm, more preferably a compound having a maximum absorption wavelength in the range of 360–480 nm. Furthermore, from the viewpoint of sensitivity, the oxime compound preferably has a high molar absorptivity at wavelengths of 365 nm or 405 nm, more preferably 1,000–300,000, even more preferably 2,000–300,000, and particularly preferably 5,000–200,000. The molar absorptivity of the compound can be determined using known methods. For example, it is preferably determined using a spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0292] As photopolymerization initiators, it is also preferred to use Irgacure OXE01 (manufactured by BASF) and / or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins BV) in combination.

[0293] As photopolymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, in the case of using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like increases, making it less prone to precipitation over time, thereby improving the storage stability of the photocurable composition. Specific examples of photoradical polymerization initiators with two or more functionalities include the compound described in paragraph 0148 of International Publication No. 2022 / 065215.

[0294] The content of photopolymerization initiator in the total solids component 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, more preferably 10% by mass or less.

[0295] The photocurable composition preferably contains 0.1 to 40 parts by weight of the specific compound described above, relative to 100 parts by weight of the photopolymerization initiator. The upper limit is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less. The lower limit is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more.

[0296] In the photocurable composition of the present invention, one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, their combined amount is preferably within the above-mentioned range.

[0297] <<Color>>

[0298] The photocurable composition of the present invention preferably contains a colorant. Examples of colorants include white colorants, black colorants, colored colorants, and infrared-absorbing colorants. In addition, in the present invention, the white colorant includes not only pure white, but also light gray (e.g., off-white, light gray, etc.) colorants that are close to white.

[0299] The colorant can be either a pigment or a dye. Pigments and dyes can be used together. The pigment can be either inorganic or organic, but organic pigments are preferred from the viewpoints of the amount of color variation, ease of dispersion, and safety. The colorant preferably contains pigment.

[0300] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. Furthermore, in this specification, the primary particle size of the pigment can be determined by observing the primary particles of the pigment using a transmission electron microscope and based on the obtained photographs. Specifically, the projected area of ​​the primary particles of the pigment is calculated, and the corresponding equivalent circle diameter is calculated as the primary particle size of the pigment.

[0301] The crystallite size, determined by the full width at half maximum (FWHM) of the peak of any crystal plane in the X-ray diffraction spectrum when the CuKα line of the pigment is used as the X-ray source, is preferably 0.1–100 nm, more preferably 0.5–50 nm, even more preferably 1–30 nm, and particularly preferably 5–25 nm.

[0302] The specific surface area of ​​the pigment is preferably 1 to 300 m². 2 / g. The lower limit is preferably 10m. 2 / g or more, preferably 30m 2 / g or more. The upper limit is preferably 250m. 2 / g or less, more preferably 200m 2 / g or less. The specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method and according to DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0303] (color material)

[0304] As color materials, examples include those with extremely high absorption wavelengths in the range of 400–700 nm. Examples include green, red, yellow, purple, blue, and orange color materials.

[0305] Examples of red pigments include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, methylimine compounds, xaton compounds, quinacridone compounds, perylene compounds, and thioindole compounds, with diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds being preferred, and diketopyrrolopyrrole compounds being more preferred. Furthermore, the red pigment is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0306] As specific examples of red pigments, we can cite the CI (colorimetric index) values ​​for 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, 1 Red pigments in the following colors: 46, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc. Furthermore, as a red pigment, compounds described in paragraph 0034 of International Patent Publication No. 2022 / 085485 and bromodione pyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2020-085947 can also be used.

[0307] As a red pigment, CI Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, and CI Pigment Red 254 and 264 are even more preferred.

[0308] Examples of green colorants include phthalocyanine compounds and squaric acid compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0309] Specific examples of green pigments include CI pigments green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, zinc halide phthalocyanine pigments with an average of 10-14 halogen atoms, 8-12 bromine atoms, and 2-5 chlorine atoms per molecule can also be used as green pigments. Specific examples include the compound described in International Publication No. 2015 / 118720. Additionally, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Application Publication No. 2020-504758 can also be used as green pigments.

[0310] As a green pigment, CI pigment green 7, 36, 58, 62, and 63 are preferred.

[0311] Examples of orange colorants include diketopyrrole compounds and azo compounds. Pigments (orange pigments) are preferred as orange colorants. Specific examples of orange colorants include CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0312] Examples of yellow pigments include azo compounds, methylimine compounds, isoindolinite compounds, pteridine compounds, quinoline compounds, and perylene compounds. Pigments (yellow pigments) are preferred as yellow pigments. Specific examples of yellow pigments include CI pigments yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, and 12. Yellow pigments in the following digits: 0, 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, etc.

[0313] As a yellow pigment, nickel azobarbiturate complexes with the following structure can also be used.

[0314] [Chemical Formula 28]

[0315]

[0316] As a yellow pigment, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, methylene dyes described in Japanese Patent Application Publication No. 2019-073695, and methylene dyes described in Japanese Patent Application Publication No. 2019-073696 can be used.

[0317] Examples of purple pigments include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. Pigments (purple pigments) are also preferred as purple pigments. Specific examples of purple pigments include CI pigments such as Purple 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0318] Examples of blue pigments include phthalocyanine compounds and squaric acid compounds, with phthalocyanine compounds being preferred. Pigments (blue pigments) are also preferred as blue pigments. Specific examples of blue pigments include CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds containing phosphorus atoms can also be used as blue pigments. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

[0319] Colored pigments can also use dyes. There are no particular restrictions on the types of dyes used; well-known dyes can be used. Examples include pyrazole azo, aniline azo, triarylmethane, anthraquinone, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanine, benzopyran, indigo, and pyrrole methylene dyes.

[0320] Pigment polymers can also be used in colored pigments. Pigment polymers are preferably dyes dissolved in a solvent. Furthermore, pigment polymers can be formed into particles. When pigment polymers are particles, they are typically used in a dispersed state in a solvent. Particle-state pigment polymers can be obtained, for example, by emulsion polymerization; specific examples include the compound and manufacturing method described in Japanese Patent Application Publication No. 2015-214682. The pigment polymer has two or more pigment structures in one molecule, preferably three or more. There is no particular upper limit, and it can be set to 100 or less. The multiple pigment structures in one molecule can be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and further preferably 6000 or more. The upper limit is more preferably 30000 or less, and further preferably 20000 or less. The pigment polymers may also include compounds described in Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, and International Publication No. 2016 / 031442.

[0321] As a colored pigment, it is possible to use the triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, the xanthones compound described in Japanese Patent Application Publication No. 2020-117638, the phthalocyanine compound described in International Patent Publication No. 2020 / 174991, the isoindoline compound or its salt described in Japanese Patent Application Publication No. 2020-160279, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, and the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-00690. The compounds represented by Formula 1 as described in Publication No. 70, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069067, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069062, the zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Unexamined Patent Publication No. 2020-180176, the phenothiazine compound described in Japanese Unexamined Patent Publication No. 2021-187913, the zinc halide phthalocyanine described in International Publication No. 2022 / 004261, and the zinc halide phthalocyanine described in International Publication No. 2021 / 250883. The colored pigment can be rotaxane, and the pigment skeleton can be used for cyclic structures of rotaxane, rod structures, or both. As a color pigment, it is also possible to use the quinoline compound represented by Formula 1 in Korean Patent Publication No. 10-2020-0030759, the polymer dye described in Korean Patent Publication No. 10-2020-0061793, the color pigment described in Japanese Patent Application Publication No. 2022-029701, the isoindoline compound described in International Patent Publication No. 2022 / 014635, the aluminum phthalocyanine compound described in International Patent Publication No. 2022 / 024926, the compound described in Japanese Patent Application Publication No. 2022-045895, the compound described in International Patent Publication No. 2022 / 050051, and the Japanese... The compounds described in Japanese Patent Application Publication No. 2020-090676, Japanese Patent Application Publication No. 2020-055956, Japanese Patent Application Publication No. 2021-031681, Japanese Patent Application Publication No. 2022-056354, U.S. Patent Application Publication No. 2021 / 0355327, International Patent Publication No. 2022 / 065357, Japanese Patent Application Publication No. 2020-045436, and Korean Patent Publication No. 10-2021-0146726.Compounds described in Japanese Patent Application Publication No. 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 Japanese Patent Application Publication No. 2022-104822, compounds described in Japanese Patent Application Publication No. 2022-096701, compounds described in Japanese Patent Application Publication No. 2020-023652, and 80-80 of the Japan Colorant Association Journal (published in 2022). The green pigment described on page 4, the compound described in Japanese Patent Application Publication No. 2022-143135, the compound described in Japanese Patent Application Publication No. 2022-140287, the compound described in International Publication No. 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyan pigment described in Korean Patent Publication No. 10-2017-0018993, the isoindoline compound described in Japanese Patent Application Publication No. 2020-180176, the compound described in Japanese Patent Application Publication No. 2023-013209, and Japanese Patent Application Publication No. 2... The compounds described in Japanese Patent Application Publication No. 023-013166, the compounds described in International Patent Application Publication No. 2023 / 286526, the compounds described in Japanese Patent Application Publication No. 2021-155746, the compounds described in Japanese Patent Application Publication No. 2021-155747, the compounds described in Japanese Patent Application Publication No. 2021-155748, the compounds described in Japanese Patent Application Publication No. 2021-155749, the compounds described in International Patent Application Publication No. 2018 / 051876, the compounds described in Japanese Patent Application Publication No. 2020-083981, and the compounds described in Japanese Patent Application Publication No. 2023-05 The compounds described in Japanese Patent Application Publication No. 6463, the compounds described in Japanese Patent Application Publication No. 2023-515473, the dioxane compounds described in Japanese Patent Application Publication No. 2022-549530, the pigment preparations described in Japanese Patent Application Publication No. 2022-061494, the diketopyrrolopyrrole pigments described in Japanese Patent Application Publication No. 2023-057917, the diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2023-061273, the phthalocyanines described in Japanese Patent Application Publication No. 2023-519314, and the quinophthalones described in Japanese Patent Application Publication No. 2023-080419, etc.

[0322] Two or more colored pigments can also be used in combination. Furthermore, when two or more colored pigments are used in combination, black can be formed by combining two or more colored pigments. Examples of such combinations include the following (1) to (7). When the photocurable composition contains two or more colored pigments and black is presented by combining two or more colored pigments, the photocurable composition of the present invention can preferably be used as a photocurable composition for forming infrared transmission filters.

[0323] (1) A method containing red and blue pigments.

[0324] (2) A method containing red, blue and yellow pigments.

[0325] (3) A method containing red, blue, yellow and purple pigments.

[0326] (4) A method containing red, blue, yellow, purple and green pigments.

[0327] (5) A method containing red, blue, yellow and green pigments.

[0328] (6) A method containing red, blue and green pigments.

[0329] (7) Methods containing yellow and purple pigments.

[0330] (White pigment)

[0331] Examples of inorganic pigments that can be used as white pigments include titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. White pigments can be those described in paragraphs 0040 to 0043 of International Publication No. 2022 / 085485.

[0332] (Black pigment)

[0333] The use of a black colorant is not particularly limited, and any known colorant can be used. The black colorant can be either inorganic or organic. Pigments are preferred. Furthermore, in this specification, a black colorant refers to a colorant that exhibits absorption across the entire wavelength range of 400–700 nm.

[0334] Examples of inorganic black pigments include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black consists of black particles containing titanium atoms, and is preferably low-order titanium oxide or titanium oxynitride. The titanium black described in paragraph 0044 of International Publication No. 2022 / 085485 can be used. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as an inorganic black pigment.

[0335] Examples of organic black pigments include bisbenzofuranone compounds, methylimine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black pigment can be any compound described in paragraph 0166 of International Patent Publication No. 2022 / 065215. Furthermore, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of Japanese Patent Application Publication No. 2017-226821, and black azo pigments described in Japanese Patent Application Publication No. 2022-121935 can also be used as organic black pigments.

[0336] The black pigments described in items 294-307 of the Journal of the Color Materials Association, Vol. 96, No. 9, 2023.

[0337] (Infrared absorbing color material)

[0338] The infrared absorbing colorant is preferably a compound that has a maximum absorption wavelength on the wavelength side longer than 700 nm. More preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1800 nm; even more preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1400 nm; even more preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1200 nm; and particularly preferably, it is a compound that has a maximum absorption wavelength in the range exceeding 700 nm and below 1000 nm. Furthermore, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm... 1 Absorbance A at the wavelength of maximum absorption 2 The ratio A 1 / A 2 Preferably, the concentration is 0.08 or less, more preferably 0.04 or less. Furthermore, the infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

[0339] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, anthocyanin compounds, squaric acid compounds, phthalocyanine compounds, naphthalene phthalocyanine compounds, quaterrylene compounds, benzophenone compounds, oxacyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, methylimine compounds, anthraquinone compounds, dibenzofuranone compounds, dithioene metal complexes, metal oxides, and metal borides. Specific examples include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, as an infrared absorbing colorant, compounds described in paragraph 0121 of International Publication No. 2022 / 065215, squaric acid compounds described in Japanese Patent Application Publication No. 2020-075959, copper complexes described in Korean Patent Publication No. 10-2019-0135217, ketone acid compounds described in Japanese Patent Application Publication No. 2021-195515, infrared absorbing pigments described in Japanese Patent Application Publication No. 2022-022070, and international publication No. 2019 / 021... The compounds described in Japanese Patent Application Publication No. 767, Japanese Patent Application Publication No. 2019-127549, Japanese Patent Application Publication No. 2022 / 059619, Japanese Patent Application Publication No. 2022-151682, Japanese Patent Application Publication No. 2022-188858, Japanese Patent Application Publication No. 2022-184710, Japanese Patent Application Publication No. 2022-189736, and Japanese Patent Application Publication No. 2023-00 The squaric acid compounds described in Japanese Patent Publication No. 4570, International Patent Publication No. 2019 / 230660, International Patent Publication No. 2020 / 218615, Japanese Patent Application Publication No. 2023-068643, Japanese Patent Application Publication No. 2023-052770, Korean Patent Publication No. 10-2022-0163680, and Japanese Patent Application Publication No. 2023-073064. Indigo monoboron complexes, phthalocyanine compounds described in Japanese Patent Application Publication No. 2023-066025, phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-041127, indigo compounds described in Japanese Patent Application Publication No. 2023-073064, indigo compounds described in Korean Patent Publication No. 10-2023-0016355, squaric acid compounds described in International Patent Publication No. 2019 / 230570, and diimine compounds described in Japanese Patent Application Publication No. 2023-095824.

[0340] The content of colorant in the total solids component of the photocurable composition is preferably 30 to 80% by mass. The upper limit is preferably 70% by mass or less, 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.

[0341] The pigment content in the total solids component of the photocurable composition is preferably 20-80% 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.

[0342] The pigment content in the colorant is preferably 20-100% by mass, more preferably 50-100% by mass, and even more preferably 70-100% by mass.

[0343] 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 their total amount is within the above-mentioned range.

[0344] <<Ammonium cationic compounds (compounds containing quaternary ammonium cations)>>

[0345] The photocurable composition of the present invention preferably contains a compound having a quaternary ammonium cation. In this manner, the adhesion or solvent resistance of the obtained film can be further improved. Hereinafter, the compound having a quaternary ammonium cation will also be referred to as an ammonium cation compound.

[0346] The ammonium cation compound can be a low-molecular-weight compound or a high-molecular-weight compound. Low-molecular-weight compounds and high-molecular-weight compounds can also be used in combination. When low-molecular-weight compounds and high-molecular-weight compounds are used in combination, the proportion of the low-molecular-weight compound is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the high-molecular-weight compound. The upper limit is preferably 12 parts by mass or less, more preferably 10 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.

[0347] When the ammonium cationic compound is a low molecular weight compound, its molecular weight is preferably 600 or less, more preferably 450 or less.

[0348] Ammonium cationic compounds, which are low-molecular-weight compounds, are preferably salts of ammonium cations and anions.

[0349] Examples of ammonium cations include those represented by formula (Am-1).

[0350] [Chemical Formula 29]

[0351]

[0352] In formula (Am-1), R Am1 ~R Am4 Each of these groups independently represents an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, or an aryl group, wherein the hydrogen atoms contained therein can be -OH, -OCO-CH=CH2, or -OCO-CH=CHR. b Substitution. Furthermore, -O-, -S-, -CO-, -NH-, or -NR can be inserted between the carbon-carbon bonds of alkyl and alkenyl groups. b -. And, R Am1 ~R Am4 They can bond with each other to form heterocycles containing nitrogen atoms in 3- to 10-membered rings. In this case, the hydrogen atoms in the heterocycle can be bonded to -R... b Or -OH substitution. R b Indicates an alkyl group having 1 to 10 carbon atoms.

[0353] Specific examples of ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, monoethyltrimethylammonium cation, monopropyltrimethylammonium cation, monobutyltrimethylammonium cation, monostearyltrimethylammonium cation, distearate dimethylammonium cation, tripearyl monomethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, dioctyldimethylammonium cation, monolauryltrimethylammonium cation, dilauryldimethylammonium cation, trilaurylmethylammonium cation, tripentylbenzylammonium cation, trihexylbenzylammonium cation, trioctylbenzylammonium cation, trilaurylbenzylammonium chloride cation, benzyldimethylstearylammonium cation, benzyldimethyloctylammonium cation, dialkyl (alkyl group is C14 to C18) dimethylammonium cation, and cations with the structures shown below.

[0354] [Chemical Formula 30]

[0355]

[0356] Examples of anions that can form salts with ammonium cations include halide anions, hydroxide anions, alkoxide anions, phenolic salt anions, amide anions (including amides substituted with acyl or sulfonyl groups), imide anions (including imides substituted with acyl or sulfonyl groups), aniline anions (including anilines substituted with acyl or sulfonyl groups), thiolate anions, bicarbonate anions, carboxylate anions, thiocarboxylate anions, dithiocarboxylate anions, hydrogen sulfate anions, sulfonate anions, dihydrogen phosphate anions, phosphate diester anions, phosphonate monoester anions, phosphonate hydrogen anions, hypophosphonate anions, nitrogen-containing heterocyclic anions, nitrate anions, hypochlorite anions, cyanide anions, cyanate anions, isocyanate anions, thiocyanate anions, isothiocyanate anions, and azide anions.

[0357] Ammonium cationic compounds can be betaine structures having both quaternary ammonium cation and anionic sites within the same molecule. Examples of such structures include those in formula (Am-1) above, where R... Am-4 Any hydrogen atom in the indicated group is substituted at the anionic site. Examples of anionic sites include the aforementioned anions, with a carboxylate anion being preferred.

[0358] When the compound containing the quaternary ammonium cation is a polymer, its weight-average molecular weight is preferably 2,000 to 50,000. The lower limit is preferably 3,000 or more, more preferably 5,000 or more. The upper limit is preferably 40,000 or less, more preferably 30,000 or less.

[0359] The ammonium cationic compound, as a polymer, is preferably a salt of a polymer having a quaternary ammonium cationic group and an anion. This ammonium cationic compound is also a material equivalent to a resin.

[0360] The anions mentioned above can be cited as examples of anions.

[0361] The quaternary ammonium cationic group present in the above polymer is preferably a group represented by formula (Cat-1).

[0362] [Chemical Formula 31]

[0363]

[0364] In the formula, R cat1 ~R cat3 Each can be represented independently as either alkyl or aryl, and * indicates a bond.

[0365] R cat1 ~R cat3 The alkyl group represented preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5.cat1 ~R cat3 The alkyl group represented is preferably straight-chain or branched, more preferably straight-chain.

[0366] R cat1 ~R cat3 The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12.

[0367] R cat1 ~R cat3 Preferably, each is an alkyl group, and the others are alkyl groups, each independently. R cat1 and R cat2 Preferably, each alkyl group is independently composed of 1 to 5 carbon atoms; more preferably, it is composed of 1 to 3 carbon atoms; further preferably, it is methyl or ethyl; and particularly preferably, it is methyl. cat3 Preferably, it 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, and even more preferably methyl or ethyl, particularly preferably methyl.

[0368] Polymers having quaternary ammonium cationic groups are preferably polymers having quaternary ammonium cationic groups on their side chains.

[0369] The weight-average molecular weight of the polymer having quaternary ammonium cationic groups is preferably 2,000 to 50,000. The lower limit is preferably 3,000 or more, more preferably 5,000 or more. The upper limit is preferably 40,000 or less, more preferably 30,000 or less.

[0370] The content of ammonium cationic compound in the total solids component of the photocurable composition is preferably 0.1 to 40% by mass.

[0371] Furthermore, when the ammonium cationic compound is a low-molecular-weight compound, the content of the ammonium cationic compound in the total solids component of the photocurable composition is preferably 0.1% to 10% by mass. The upper limit is preferably 8% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more.

[0372] Furthermore, when the ammonium cationic compound is a polymer, the content of the ammonium cationic compound in the total solids component of the photocurable composition is preferably 5 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.

[0373] In the photocurable composition of the present invention, one type of ammonium cationic compound may be used, or two or more types may be used. When two or more types are used, their combined amount is preferably within the above-mentioned range.

[0374] <<Solvent>>

[0375] The photocurable composition of the present invention preferably contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details regarding these solvents, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Furthermore, cyclic alkyl-substituted ester solvents and cyclic alkyl-substituted ketone solvents are also 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, and propylene glycol. Monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-dimethyldiacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (as an alternative name, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropanol, etc. However, sometimes for environmental reasons, it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents (for example, relative to the total amount of organic solvents, it can be set to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less).

[0376] The metal content of the organic solvent is preferably low. For example, the metal content of the organic solvent is preferably below 10 parts per billion (ppb). Organic solvents with a metal content at the ppt (parts per trillion) level can be used as needed, such organic solvents are provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0377] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, membrane distillation, etc.) or filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0378] Organic solvents can contain isomers (compounds with the same number of atoms but different structures). Furthermore, they can contain only one isomer or multiple isomers.

[0379] The peroxide content in the organic solvent is preferably below 0.8 mmol / L, and more preferably substantially free of peroxide.

[0380] The solvent content in the photocurable composition is preferably 10-95% by mass, more preferably 20-90% by mass, and even more preferably 30-90% by mass.

[0381] From an environmental perspective, the photocurable composition of the present invention is preferably substantially free of environmentally restricted substances. Furthermore, in the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are registered as environmentally restricted substances under REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulations, PRTR (Pollutant Release and Transfer Register) law, and VOC (Volatile Organic Compounds) restrictions, and their usage and treatment methods are strictly limited. These compounds are sometimes used as solvents in the various components used in the manufacture of the photocurable composition, and sometimes they are mixed into the photocurable composition as residual solvents. From the perspective of human safety and the environment, it is preferable to minimize these substances as much as possible. One method for reducing environmentally restricted substances is to heat and depressurize the system to a temperature above the boiling point of the substance, and then distill it off within the system to reduce its concentration. Furthermore, when distilling off small amounts of environmentally restricted substances, azeotropic distillation with a solvent having a similar boiling point is useful to improve efficiency. Additionally, when the substance contains compounds with free radical polymerization potential, depressurized distillation can be performed by adding polymerization inhibitors to suppress free radical polymerization reactions that could lead to intermolecular crosslinking. These distillation removal methods can be performed at any stage, including the raw material stage, the product stage (e.g., a polymerized resin solution or a multifunctional monomer solution), or the stage where these compounds are mixed to form a photocurable composition.

[0382] <<Pigment Derivatives>>

[0383] The photocurable composition of the present invention can contain pigment derivatives. Pigment derivatives can be used as dispersing agents. Dispersing agents are materials used to improve the dispersibility of pigments or other colorants in a photocurable composition. Examples of pigment derivatives include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a base group.

[0384] Examples of pigment structures mentioned above include quinoline pigment structures, benzimidazolone pigment structures, benzisoindole pigment structures, benzothiazole pigment structures, imine pigment structures, squaric acid pigment structures, ketoneonium pigment structures, oxacyanine pigment structures, pyrrolopyrrole pigment structures, diketopyrrolopyrrole pigment structures, azo pigment structures, methylimine pigment structures, phthalocyanine pigment structures, naphthylphthalocyanine pigment structures, anthraquinone pigment structures, quinacridone pigment structures, dioxazine pigment structures, violane pigment structures, perylene pigment structures, thiazine indigo pigment structures, thioindoleline pigment structures, isoindoleline pigment structures, isoindolelineone pigment structures, quinophthalone pigment structures, dithiol pigment structures, triarylmethane pigment structures, and pyrrolemethylene pigment structures.

[0385] Examples of acid groups include carboxyl, sulfonyl, phosphate, boric acid, carboxylic acid amide, sulfonamide, imide, and their salts. Examples of atoms or groups constituting salts include alkali metal ions (Li...). + Na + K + (etc.), alkaline earth metal ions (Ca 2+ Mg 2+ (etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As the carboxylic acid amide group, it is preferably composed of -NHCOR X1 The group indicated. As a sulfonamide group, it is preferably composed of -NHSO2R. X2 The group indicated. As an imide group, it is preferably composed of -SO2NHSO2R. X3 -CONHSO2R X4 -CONHCOR X5 or -SO2NHCOR X6 The indicated group is more preferably -SO2NHSO2R. X3 R X1 ~R X6 Each can be represented independently as either alkyl or aryl. R X1 ~R X6 The alkyl and aryl groups may have substituents. Halogen atoms are preferred as substituents, and fluorine atoms are more preferred.

[0386] Examples of bases include amino groups, pyridyl groups and their salts, ammonium salts, and phthalimide methyl groups. Examples of atoms or groups that constitute salts include hydroxide ions, halide ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0387] Specific examples of pigment derivatives include the compounds described in paragraphs 0037-0054 of International Publication No. 2016 / 035695, the compounds described in paragraphs 0061-0086 of International Publication No. 2017 / 146092, the compounds described in paragraphs 0017-0068 of International Publication No. 2018 / 230387, and the compounds described in paragraphs 0085-0066 of International Publication No. 2020 / 054718. The compounds described in paragraph 099, the compounds described in paragraph 0099 of International Publication No. 2020 / 054718, the compounds described in paragraph 0124 of International Publication No. 2022 / 085485, the benzimidazolone compounds or salts thereof described in Japanese Patent Application Publication No. 2018-168244, and the compounds having an isoindoline skeleton of general formula (1) described in Japanese Patent No. 6996282, etc.

[0388] The content of pigment derivatives relative to 100 parts by weight of pigment is preferably 1 to 50 parts by weight. The lower limit is preferably 3 parts by weight or more, more preferably 5 parts by weight or more. The upper limit is preferably 40 parts by weight or less, more preferably 30 parts by weight or less. The photocurable composition may contain only one pigment derivative or two or more pigment derivatives. When it contains two or more photopolymerization initiators, their total amount is preferably within the above-mentioned range.

[0389] <<Polyalkylimine>>

[0390] The photocurable compositions of the present invention may also contain polyalkylene imides. Polyalkylene imides can be used, for example, as dispersants for pigments. Polyalkylene imides refer to polymers formed by ring-opening polymerization of alkylene imides. Polyalkylene imides are preferably polymers having branched structures containing primary, secondary, and tertiary amino groups, respectively. The number of carbon atoms in the alkylene imides is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0391] The molecular weight of the polyalkylene imide 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, further preferably 10,000 or less, and particularly preferably 2,000 or less. Furthermore, regarding the molecular weight of the polyalkylene imide, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imide is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number-average molecular weight value determined by the boiling point elevation method is used. Furthermore, when the boiling point elevation method is also not feasible or difficult to determine, the number-average molecular weight value determined by the viscosity method is used. Furthermore, when the viscosity method is also not feasible or difficult to determine, the number-average molecular weight value from the polystyrene conversion value determined by GPC (gel permeation chromatography) is used.

[0392] The amine value of the polyalkylene imide is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0393] Specific examples of alkylene imides include ethyleneimine, propyleneimine, 1,2-buteneimine, and 2,3-buteneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. Polyalkylene imides are particularly preferred to be polyethyleneimine. Furthermore, relative to the total amount of primary, secondary, and tertiary amino groups, polyethyleneimine preferably contains 10 mol% or more of primary amino groups, more preferably 20 mol% or more of primary amino groups, and even more preferably 30 mol% or more of primary amino groups. Commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by NIPPON SHOKUBAI CO., LTD.).

[0394] The content of polyalkylene imide in the total solids component of the photocurable composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Furthermore, relative to 100 parts by mass of pigment, the content of polyalkylene imide is preferably 0.5 to 20 parts by mass. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imide may be used, or two or more types may be used. When two or more types are used, their combined amount is preferably within the above-mentioned range.

[0395] <<Compounds with cyclic ether groups>>

[0396] The photocurable composition of the present invention can contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups, oxacyclobutyl groups, etc. The epoxy group can be an alicyclic epoxy group. Furthermore, an alicyclic epoxy group refers to a monovalent functional group having a cyclic structure formed by the fusion of an epoxy ring and a saturated hydrocarbon ring. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups per molecule, preferably compounds having two or more epoxy groups. The epoxy compound is preferably a compound having 1 to 100 epoxy groups per molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.

[0397] As compounds having cyclic ether groups, compounds described in Japanese Patent Application Publication No. 2013-011869 (paragraphs 0034-0036), Japanese Patent Application Publication No. 2014-043556 (paragraphs 0147-0156), Japanese Patent Application Publication No. 2014-089408 (paragraphs 0085-0092), Japanese Patent Application Publication No. 2017-179172, cyclohexane-type epoxy resins described in Japanese Patent Application Publication No. 2021-195421, and cyclohexane-type epoxy resins described in Japanese Patent Application Publication No. 2021-195422 can also be used.

[0398] Compounds having cyclic ether groups can be low molecular weight compounds (e.g., molecular weight less than 2000, and further, less than 1000) or macromolecules (e.g., molecular weight 1000 or more, and in the case of polymers, weight-average molecular weight 1000 or more). The weight-average molecular weight of compounds having cyclic ether groups is preferably 200 to 100,000, 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.

[0399] Commercially available examples of compounds containing cyclic ether groups include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF CORPORATION, polymers containing epoxy groups).

[0400] The content of compounds having cyclic ether groups in the total solids composition 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. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. Only one compound having cyclic ether groups may be used, or two or more compounds may be used. When two or more compounds are used, their combined amount is preferably within the above-mentioned range.

[0401] <<Curing Accelerator>>

[0402] The photocurable composition of the present invention can contain a curing accelerator. Examples of curing accelerators include thiols, hydroxymethyl compounds, amine compounds, phosphonium salts, amidine salts, amide compounds, alkali-generating agents, isocyanate compounds, alkoxysilane compounds, and onium salts. Specific examples of curing accelerators include compounds described in paragraph 0164 of International Publication No. 2022 / 085485 and compounds described in Japanese Patent Application Publication No. 2021-181406. The content of the curing accelerator in the total solids component of the photocurable composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

[0403] <<Ultraviolet Absorber>>

[0404] The photocurable composition of the present invention can contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and benzoyl compounds. Specific examples of such compounds include those described in International Patent Publication No. 2022 / 085485, paragraph 0179; reactive triazine ultraviolet absorbers described in Japanese Patent Application Publication No. 2021-178918; ultraviolet absorbers described in Japanese Patent Application Publication No. 2022-007884; compounds described in Korean Patent Publication No. 10-2022-0014454; and compounds described in Japanese Patent Application Publication No. 2023-013321. The content of the ultraviolet absorber in the total solids component of the photocurable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. One type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that their combined dosage is within the range mentioned above.

[0405] <<Polymerization Inhibitor>>

[0406] The photocurable composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solids component of the photocurable composition is preferably 0.0001 to 5% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. When there are two or more types, the total amount is preferably within the above range.

[0407] <<Silane Coupling Agents>>

[0408] The photocurable composition of the present invention can contain a silane coupling agent. Examples of silane coupling agents include silane compounds having a hydrolyzable group, preferably silane compounds having a hydrolyzable group and other functional groups. A hydrolyzable group refers to a substituent that can form a siloxane bond by directly bonding with a silicon atom and by at least one of a hydrolysis reaction and a fusion reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, etc., preferably alkoxy groups. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Furthermore, examples of functional groups other than the hydrolyzable group include vinyl, (meth)allyl, (meth)acryloyl, mercapto, epoxy, oxetyl, amino, urea, sulfide group, isocyanate group, phenyl, etc., preferably amino, (meth)acryloyl, and epoxy groups. Specific examples of silane coupling agents include the compounds described in paragraph 0177 of International Patent Publication No. 2022 / 085485 and the compounds described in Japanese Patent Application Publication No. 2019-183020. The content of the silane coupling agent in the total solids component 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. There may be only one type of silane coupling agent, or there may be two or more types. When there are two or more types, the total amount is preferably within the above range.

[0409] <<Surfactants>>

[0410] The photocurable composition of the present invention can contain a surfactant. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants, can be used as surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant, and more preferably a silicone surfactant. Regarding surfactants, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, the contents of which are incorporated herein by reference.

[0411] As a fluorinated surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485 can be used.

[0412] As a nonionic surfactant, the compound described in paragraph 0174 of International Publication No. 2022 / 085485 can be cited as an example.

[0413] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BYK Chemie GmbH). Furthermore, silicone surfactants can also use compounds with the following structures.

[0414] [Chemical Formula 32]

[0415]

[0416] The surfactant content in the total solids component of the photocurable composition is preferably 0.001% to 5.0% by mass, more preferably 0.005% 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, the total amount is preferably within the above range.

[0417] <<Antioxidants>>

[0418] The photocurable composition of the present invention can contain an antioxidant. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples of phenolic antioxidants include hindered phenolic compounds. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. The aforementioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Antioxidants are also preferably compounds having a phenolic group and a phosphite group within the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphatahept-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphatahept-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl 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, ADEKASTAB AO-330 (all manufactured by ADEKA CORPORATION), and JP-650 (manufactured by JOHOKU CHEMICAL CO., LTD.). The antioxidant can also be the compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, the compounds described in International Publication No. 2017 / 006600, the compounds described in International Publication No. 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The antioxidant content in the total solids component of the photocurable composition is preferably 0.01-20% by mass, more preferably 0.3-15% by mass. Only one antioxidant can be used, or two or more antioxidants can be used. When two or more antioxidants are used, their combined amount is preferably within the above range.

[0419] <<Other Ingredients>>

[0420] The photocurable compositions of the present invention may, as needed, contain sensitizers, plasticizers, and other additives (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, film properties and other characteristics can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485.

[0421] To adjust the refractive index of the obtained film, the photocurable composition of the present invention may contain a metal oxide. Examples of metal oxides include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. Furthermore, the core may be hollow.

[0422] The photocurable composition of the present invention may contain a lightfastness modifier. Examples of lightfastness modifiers include compounds described in paragraph 0183 of International Publication No. 2022 / 085485.

[0423] The photocurable composition of the present invention is preferably substantially free of terephthalate. Here, "substantially free" means that the content of terephthalate 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.

[0424] From an environmental perspective, the melamine content in the photocurable composition of the present invention is preferably less than 10,000 ppm by mass.

[0425] The free metal content of the photocurable composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals or halogens in the photocurable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchanged resins.

[0426] From an environmental perspective, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, is sometimes restricted. In the photocurable composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acids (especially perfluoroalkyl sulfonic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, and perfluoroalkyl carboxylic acids (especially perfluoroalkyl carboxylic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, relative to the total solids content of the photocurable composition, 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. The photocurable composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using compounds that can replace perfluoroalkyl sulfonic acids and their salts, and compounds that can replace perfluoroalkyl carboxylic acids and their salts, a photocurable composition substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, can be selected. As alternatives to the restricted compounds, examples include compounds excluded from the restrictions due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the foregoing does not preclude the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. The photocurable compositions of the present invention may contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, within the maximum permissible range.

[0427] The moisture content of the photocurable composition of the present invention is typically 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The moisture content can be determined using the Karl Fischer method.

[0428] The photocurable composition of the present invention can be used to adjust the viscosity for purposes such as adjusting film surface (flatness, etc.) and film thickness. The viscosity value can be appropriately selected as needed, but for example, at 25°C, it is preferably 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s. As a method for measuring viscosity, for example, a cone-plate viscometer can be used, and the measurement can be performed at a temperature adjusted to 25°C.

[0429] <<Containment Container>>

[0430] There are no particular limitations on the container used for the photocurable composition, and any known container can be used. Furthermore, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.

[0431] <Preparation Method of Photocurable Composition>

[0432] The photocurable composition of the present invention can be prepared by mixing the aforementioned components. In preparing the photocurable composition, all components can be simultaneously dissolved and / or dispersed in a solvent, or, as needed, each component can be appropriately prepared as a solution or dispersion of two or more parts, which are then mixed during use (coating) to prepare the photocurable composition.

[0433] When preparing a photocurable composition, a process for dispersing pigments is preferred. Examples of mechanical forces used for pigment dispersion in this process include compression, extrusion, impact, shearing, and cavitation. Specific examples of these processes include bead milling, grinding, roller milling, ball milling, paint stirring, microjet milling, high-speed impeller milling, sand milling, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. Furthermore, in the grinding of pigments in bead milling, it is preferable to perform the process under conditions that improve grinding efficiency by using small-diameter beads and increasing the bead filling rate. After grinding, it is preferable to remove coarse particles by filtration, centrifugation, or other methods. Furthermore, regarding the manufacturing process and dispersing machine for disperse pigments, the processes and dispersing machines described in "Complete Collection of Dispersion Technology, published by JOHOKIKO CO.,LTD., July 15, 2005" or "Comprehensive Data Collection on Dispersion Technology and Practical Industrial Applications Centered on Suspension (Solid / Liquid Dispersion Systems), published by the Business Development Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893, are preferred. In the manufacturing process of disperse pigments, particle refinement can be achieved through a salt milling process. The materials, equipment, and processing conditions used in the salt milling process can be referenced, for example, in Japanese Patent Application Publication Nos. 2015-194521 and 2012-046629. Examples of materials for the beads used for dispersion include zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, the beads can also be made of inorganic compounds with a Mohs hardness of 2 or higher. The photocurable composition may contain 1 to 10,000 ppm of the aforementioned beads.

[0434] When preparing a photocurable composition, it is preferable to filter the composition with a filter in order to remove impurities or reduce defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0435] <Membrane>

[0436] The membrane of the present invention is obtained from the photocurable composition of the present invention described above. The membrane of the present invention can be used in filters such as color filters, infrared transmission filters, and infrared cutoff filters.

[0437] The film thickness of the membrane of the present invention can be appropriately adjusted according to the purpose. For example, the film 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.

[0438] When the film of the present invention is used as a color filter, the film preferably has a green, red, blue, cyan, magenta, or yellow hue. Furthermore, the film of the present invention can preferably be used as a colored pixel in a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0439] <Membrane Manufacturing Method>

[0440] Next, a method for manufacturing the film of the present invention will be described. The film of the present invention can be manufactured by coating the photocurable resin composition of the present invention. In the method for manufacturing the film, a step of forming a pattern (pixel) is preferably also included. As a method for forming the pattern (pixel), photolithography can be cited.

[0441] The pattern formation using photolithography preferably includes the following steps: a step of forming a composition layer on a support using the photocurable resin composition of the present invention; a step of exposing the composition layer in a patterned manner; and a step of developing to remove the unexposed portions of the composition layer to form a pattern (pixel). If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (pixel) may also be provided (post-baking step).

[0442] In the process of forming the composition layer, the photocurable composition of the present invention is used to form the composition layer on a support. There are no particular limitations on the support, and it can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. Furthermore, charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) films, transparent conductive films, etc., can also be formed on the silicon substrate. Sometimes, a black matrix is ​​formed on the silicon substrate to isolate each pixel. Furthermore, a base layer can be provided on the silicon substrate to improve adhesion to the upper layer, prevent material diffusion, or planarize the substrate surface. When measured with diiodomethane, the surface contact angle of the base layer is preferably 20–70°. And when measured with water, it is preferably 30–80°.

[0443] As a coating method for photocurable compositions, known methods can be used. Examples include drop casting; slot coating; spraying; roller coating; spin coating; cast coating; slot and spin coating; pre-wetting (e.g., the method described in Japanese Patent Application Publication No. 2009-145395); inkjet printing (e.g., on-demand, piezoelectric, thermal), nozzle ejection, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, and various other printing methods; transfer methods using molds, etc.; nanoimprinting, etc. Furthermore, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.

[0444] The composition layer formed on the support can be dried (pre-baked). When the film is manufactured by a low-temperature process, pre-baking may not be necessary. When pre-baking is performed, the pre-baking temperature is preferably below 150°C, more preferably below 120°C, and even more preferably below 110°C. The lower limit can be set to 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a heating plate, oven, or the like.

[0445] Next, the composition layer is exposed in a pattern (exposure process). For example, using a stepper or scanning exposure machine, the composition layer is exposed through a mask with a specified mask pattern, thereby enabling patterned exposure. This allows the exposed portion to be cured.

[0446] Examples of radiation (light) that can be used during exposure include gamma rays and i-rays. Furthermore, light with wavelengths below 300 nm can also be used (preferably light with wavelengths of 180–300 nm). Examples of light with wavelengths below 300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Additionally, light sources with wavelengths above 300 nm can also be used.

[0447] Furthermore, during exposure, exposure can be performed by continuous illumination or by pulsed illumination (pulse exposure). In addition, pulse exposure is an exposure method that involves repeatedly illuminating and pausing light for short periods of time (e.g., less than milliseconds).

[0448] The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm. 2 More preferably, it is 0.05–1.0 J / cm³. 2Regarding the oxygen concentration during exposure, it can be appropriately selected. Besides exposure under atmospheric conditions, it can also be performed in low-oxygen environments with an oxygen concentration below 19% by volume (e.g., 15% by volume, 5% by volume, or virtually oxygen-free), or in high-oxygen environments with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, typically from 1000 W / m². 2 ~100000W / m 2 (For example, 5000W / m) 2 15000W / m 2 Or 35000W / m 2 The range of oxygen concentration and illuminance can be selected. These conditions can be appropriately combined; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m² can be set. 2 Oxygen concentration 35% by volume and illuminance 20000 W / m² 2 wait.

[0449] Next, the unexposed portions of the composition layer are removed by development to form a pattern (pixel). The unexposed portions of the composition layer can be removed by developing a developer. As a result, the unexposed portions of the composition layer from the exposure process dissolve in the developer, leaving only the photocured portion. The temperature of the developer is preferably, for example, 20–30°C. The development time is preferably 20–180 seconds. Furthermore, to improve residue removal, the process of repeatedly discarding the developer every 60 seconds and then supplying fresh developer can be repeated multiple times.

[0450] Developers may include organic solvents, alkaline developers, etc., and alkaline developers are preferred. Regarding the developer and the post-development cleaning (rinsing) method, the developer or cleaning method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0451] After development, and following drying, it is preferable to perform additional exposure treatment or heat treatment (post-baking). Additional exposure treatment or post-baking is a curing treatment after development to ensure complete curing. The heating temperature during post-baking is preferably 100–300°C, more preferably 200–270°C. The developed film can be post-baked continuously or intermittently using heating means such as hot plates, convection ovens (hot air circulating dryers), or high-frequency heaters to achieve the above conditions. When performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of 400 nm or less. Furthermore, the additional exposure treatment can also be performed using the method described in Korean Patent Publication No. 10-2017-0122130.

[0452] <Filter>

[0453] The film of the present invention can be used in filters. Examples of filters include color filters, infrared cut-off filters, and infrared transmission filters, with color filters being preferred. Color filters preferably have the film of the present invention as their pixels, and more preferably have the film of the present invention as their colored pixels.

[0454] A protective layer can also be provided on the surface of the membrane of the present invention in the filter. By providing a protective layer, various functions such as oxidation resistance, low reflectivity, hydrophilicity / hydrophobicity, and shielding of light of specific wavelengths (ultraviolet, infrared, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of methods for forming the protective layer include methods of forming by coating a resin composition for forming a protective layer, chemical vapor deposition, and methods of attaching a pre-formed resin with an adhesive. Examples of components constituting the protective layer include (meth)acrylic resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyaryl ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, polyurethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluoropolymers, polyacrylonitrile resins, cellulose resins, Si, C, W, Al₂O₃, Mo, SiO₂, and Si₂N₄, and more than two of these components may be included. For example, in the case of a protective layer intended to block oxidation, the protective layer preferably contains polyol resins, SiO₂, and Si₂N₄. Furthermore, in the case of a protective layer intended to reduce reflectivity, the protective layer preferably contains (meth)acrylic resins and fluoropolymers.

[0455] When a resin composition is coated to form a protective layer, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition used to form 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 used to form the protective layer. When the protective layer is formed by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma-enhanced chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

[0456] Depending on the requirements, the protective layer may also contain additives such as organic / inorganic microparticles, absorbers of specific wavelengths of light (e.g., ultraviolet, infrared, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants. Examples of organic / inorganic microparticles include, for instance, polymeric microparticles (e.g., silicone resin microparticles, polystyrene microparticles, melamine resin microparticles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers can be used for the specific wavelengths of light. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass relative to the total mass of the protective layer, more preferably 1 to 60% by mass.

[0457] As a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Publication No. 2017-151176 may also be used.

[0458] Filters can also have the following structure: pixels are embedded in spaces separated by partitions, for example, in a grid pattern.

[0459] Solid-state imaging element

[0460] The solid-state imaging element of the present invention has the film of the present invention as described above. As for the structure of the solid-state imaging element, there are no particular limitations as long as it has the film of the present invention and functions as a solid-state imaging element; for example, the following structures can be cited.

[0461] The solid-state imaging element has the following structure: On a substrate, there are multiple photodiodes constituting the light-receiving area of ​​the solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transmission electrode made of polysilicon, etc. A light-shielding film with openings only for the light-receiving portions of the photodiodes is present on the photodiodes and the transmission electrode. A device protective film made of silicon nitride, etc., is formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is present on the device protective film. Furthermore, it can have a structure with a light-concentrating mechanism (e.g., a microlens, etc. The same applies hereinafter) on the device protective film and on the underside (closer to the substrate) of the color filter, or a structure with a light-concentrating mechanism on the color filter itself. The color filter can also have a structure in which each colored pixel is embedded in a space divided by partitions, for example, in a grid pattern. In this case, the partitions are preferably of a low refractive index relative to each colored pixel. Examples of camera devices with this structure include those described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Application Publication No. 2019-211559, an ultraviolet absorption layer can be provided within the structure of the solid-state camera element to improve lightfastness. Camera devices equipped with the solid-state camera element of the present invention can be used not only in digital cameras or electronic devices with camera functions (such as mobile phones), but also as vehicle cameras or surveillance cameras.

[0462] <Image display device>

[0463] The image display device of the present invention includes the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. Definitions of image display devices and detailed descriptions of various image display devices are described, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989). Furthermore, liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, liquid crystal display devices applicable to the various methods described in "Next-Generation Liquid Crystal Display Technology" can be applied.

[0464] Example

[0465] The present invention will be specifically described below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Furthermore, Ph in the following structural formulas represents a phenyl group.

[0466] <Resin Evaluation>

[0467] (Weight-average molecular weight (Mw))

[0468] The weight-average molecular weight (Mw) of the resin was calculated by GPC (Gel Permeation Chromatography) under the following test conditions.

[0469] Device: HLC-8220GPC (manufactured by TOSOH CORPORATION)

[0470] Detector: Differential refractometer (RI detector)

[0471] Pre-string: TSKGUARDCOLUMN MP (XL) 6mm × 40mm (manufactured by TOSOH CORPORATION)

[0472] Sample side column: Directly connect the following 4 columns (all manufactured by TOSOH CORPORATION)

[0473] TSK-GEL Multipore-HXL-M 7.8mm×300mm

[0474] Reference side column: Same as the sample side column

[0475] Thermostatic bath temperature: 40℃

[0476] Mobile phase: Tetrahydrofuran

[0477] Sample-side mobile phase flow rate: 1.0 mL / min

[0478] Reference side mobile phase flow rate: 0.3 mL / min

[0479] Sample concentration: 0.1% by mass

[0480] Sample injection volume: 100 μL

[0481] Data acquisition time: 16–46 minutes after sample injection

[0482] Sampling interval: 300ms (milliseconds)

[0483] -Acid Value-

[0484] The acid value of the resin was determined by neutralization titration with sodium hydroxide. Specifically, for the solution obtained by dissolving the resin in a solvent, potentiometric titration was performed using an aqueous sodium hydroxide solution, and the millimoles of acid contained in 1g of the solid component of the resin were calculated. Then, the acid value of the resin was determined by multiplying this value by the molecular weight of potassium hydroxide (KOH), which is 56.1.

[0485] (C=C value (value of groups containing olefinic unsaturated bonds))

[0486] The C=C value (the value of groups containing olefinic unsaturated bonds) of a resin is calculated based on the raw materials used in the synthesis of the resin.

[0487] <Preparation of Resin Solution>

[0488] [Manufacturing Example 1-1] Manufacturing of Resin Solution (B-1)

[0489] A separate flask with a cooling tube was prepared as the reaction vessel. On the other hand, a monomer dropping vessel was prepared by thoroughly mixing 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 dimethyl 2,2'-azobis(2-methylpropionic acid) (low metal grade) (manufactured by FUJIFILM Wako Pure Chemical Corporation, "V-601HP"), 435 parts by mass of cyclohexanone, and 5.33 parts by mass of n-dodecanethiol (hereinafter referred to as "n-DM"). 49 parts by mass of cyclohexanone was added to the reaction vessel and purged with nitrogen. The vessel was then heated in an oil bath with stirring until the temperature reached 75°C. After the temperature of the reaction vessel stabilized at 75°C, the dropping from the monomer dropping vessel to the reaction vessel began. The dropping was carried out over 150 minutes while maintaining the temperature at 75°C. 120 minutes after the addition is complete, begin heating the reaction vessel to 90°C. Maintain this temperature for 2 hours, then cool the reaction solution to room temperature.

[0490] After the polymerization reaction was completed, under air, 3.09 parts by mass of N,N-dimethyldodecylamine was added as an amine compound, 0.5 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, followed by 37.43 parts by mass of glycidyl methacrylate (hereinafter referred to as "GMA") and 96 parts by mass of cyclohexanone. The reaction solution was then heated to 90°C. After maintaining the temperature at 90°C for 6 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was drained into a mixture of 10,000 parts by mass of methanol and 2,500 parts by mass of water. The precipitated solid (polymer) was filtered off and washed twice with 500 parts by mass of water. The washed solid was dried under air at 50°C for 18 hours to obtain resin B-1 with the following structure. The obtained resin B-1 has a weight-average molecular weight (Mw) of 12,000, an acid value of 32 mg KOH / g, and a C=C value of 1.13 mmol / g.

[0491] The resin B-1 obtained through the above process was added to propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and the resin concentration (solid component concentration) of the final resin solution was adjusted to 30% to produce the resin solution (B-1).

[0492] [Chemical Formula 33]

[0493]

[0494] [Manufacturing Examples 1-2] Manufacturing of Resin Solution (B-2)

[0495] A separate flask equipped with a cooling pipe was prepared as the reaction vessel. On the other hand, a monomer dropping tank was prepared by stirring and mixing 30.7 parts by mass of 2,2'-[oxybis(methylene)]bis-2-acrylate, 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"). A chain transfer agent dropping tank was prepared by stirring and mixing 8 parts by mass of n-DM and 32 parts by mass of DMDG. 375 parts by mass of DMDG was added to the reaction vessel and purged with nitrogen. The reaction vessel was heated in an oil bath while stirring until the temperature reached 90°C. After the temperature of the reaction vessel stabilized at 90°C, the dropping of monomers and chain transfer agents from the monomer dropping tank and chain transfer agent dropping tank into the reaction vessel began. The addition was carried out dropwise over 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the addition ended, the temperature was raised to bring the reaction vessel to 110°C. After maintaining this temperature for 3 hours, the gas inlet tube was connected to a split flask, and bubbling of a 5 / 95 (v / v) oxygen / nitrogen mixture was started. Next, 50.9 parts by mass of GMA, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (hereinafter referred to as "MBMTB"), and 0.8 parts by mass of triethylamine (hereinafter referred to as "TEA") were added to 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 were added to the reaction solution, and the solution was cooled to room temperature. 1000 parts by weight of water were added to the cooled reaction solution, and the precipitated solid (polymer) was filtered off. The filtered solid was washed twice with 100 parts by weight of ethanol and once with 500 parts by weight of water to obtain resin B-2 with the following structure. The obtained resin B-2 has a weight-average molecular weight (Mw) of 18000, an acid value of 32 mg KOH / g, and a C=C value of 1.42 mmol / g.

[0496] The resin B-2 obtained through the above process was added to PGMEA, and the resin concentration (solid component concentration) of the final resin solution was adjusted to 30% to produce the resin solution (B-2).

[0497] [Chemical Formula 34]

[0498]

[0499] [Manufacturing Examples 1-3] Manufacturing of Resin Solution (B-3)

[0500] 30.4 parts by mass of a macromonomer represented by the following formula (MM), 51 parts by mass of ω-carboxy-polycaprolactone monoacrylate (manufactured by TOAGOSEI CO., LTD., ARONIX M-5300), and PGMEA were introduced into a three-necked flask to obtain a mixture. The mixture was stirred while nitrogen was purged.

[0501] [Chemical Formula 35]

[0502]

[0503] Next, the mixture was heated to 75°C while nitrogen gas flowed through the flask. Then, 0.82 parts by mass of n-DM were added to the mixture, followed by 0.43 parts by mass of 2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILMWako Pure Chemical Corporation, V-601), and the polymerization reaction was initiated. After heating the mixture at 75°C for 2 hours, another 0.43 parts by mass of 2,2'-azobis(2-methylpropionate) was 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 then completed using the above steps. After the polymerization reaction was completed, 9.6 parts by mass of dimethyldodecylamine was added as an amine compound and 0.3 parts by mass of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added as a polymerization inhibitor under air. Then, 9 parts by mass of 4-hydroxybutylacrylate glycidyl ether (4HBAGE) was added dropwise.

[0504] After the addition was complete, the reaction was continued at 90°C in air for 24 hours. The reaction was then confirmed to be complete by acid value determination, and the reaction solution was cooled to room temperature. 1000 parts by weight of water were added to the cooled reaction solution, and the precipitated solid (polymer) was filtered off. The filtered solid was washed twice with 100 parts by weight of ethanol and once with 500 parts by weight of water to obtain resin B-3 with the following structure. The obtained resin B-3 has a weight-average molecular weight (Mw) of 17200, an acid value of 70 mg KOH / g, and a C=C value of 0.50 mmol / g.

[0505] The resin B-3 obtained through the above process was added to PGMEA, and the resin concentration (solid component concentration) of the final resin solution was adjusted to 30% to produce the resin solution (B-3).

[0506] [Chemical Formula 36]

[0507]

[0508] [Manufacturing Examples 1-4] Manufacturing of Resin Solution (B-4)

[0509] Eight 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 added to a reaction vessel equipped with a gas inlet pipe, thermometer, condenser, and stirrer. After purging with nitrogen, the reaction was carried out at 120°C for 5 hours (first step). The acid value confirmed that over 95% of the anhydride was half-esterified. Next, 30 parts by mass of methyl methacrylate, 10 parts by mass of tert-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 added. The reaction vessel was heated to 80°C, and 1 part by mass of 2,2'-azobis(2,4-dimethylpentanonitrile) was added, and the reaction was carried out for 12 hours (second step). The solid content confirmed that 95% of the reaction had occurred. Next, the flask was purged with air, and 35.0 parts by weight of 2-methacryloyloxyethyl isocyanate and 0.1 parts by weight of hydroquinone were added. The mixture was then reacted at 70°C for 4 hours (third step). Infrared absorption spectrometry was used to confirm the presence of the isocyanate group at 2270 cm⁻¹. -1 After the peak disappeared, the reaction solution was cooled to obtain resin B-4 with the following structure. The obtained resin B-4 has an acid value of 40 mg KOH / g, a weight-average molecular weight of 12000, and a C=C value of 1.44 mmol / g.

[0510] [Chemical Formula 37]

[0511]

[0512] In formula (B-4), either *1 or *2 bonds with *5 or *6 to form a polyester backbone, and the other bonds with *3 or *4 to form a polyester backbone. Either *3 or *4 bonds with *1 or *2 to form a polyester backbone, and the other bonds with an OH group to form a carboxylic acid. Either *5 or *6 bonds with *1 or *2 to form a polyester backbone, and the other bonds with an OH group to form a carboxylic acid.

[0513] The resin B-4 obtained through the above process was added to PGMEA, and the resin concentration (solid component concentration) of the final resin solution was adjusted to 30% to produce the resin solution (B-4).

[0514] [Manufacturing Examples 1-5] Manufacturing of Resin Solution (B-5)

[0515] According to the method for synthesizing resin (B3-1) solution described in paragraph 0350 of Japanese Patent Application Publication No. 2023-050814, resin B-5 with the following structure was obtained. The obtained resin B-5 has an amine value of 170 mg KOH / g and a weight-average molecular weight of 20,000.

[0516] The resin B-5 obtained through the above process was added to PGMEA, and the resin concentration (solid component concentration) of the final resin solution was adjusted to 30% to produce the resin solution (B-5).

[0517] [Chemical Formula 38]

[0518]

[0519] <Manufacturing of Micronized Pigments>

[0520] [Manufacturing Example 2-1]

[0521] (Manufacturing of micronized pigment (PR254M))

[0522] 100 parts by weight of CI Pigment Red 254 (BASF "B-CF"), 1200 parts by weight of sodium chloride, and 120 parts by weight of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by INOUE MFG., INC.) and kneaded at 60°C for 4 hours. The resulting mixture was then added to 3000 parts by weight of warm water and stirred for 1 hour to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried overnight at 80°C to obtain a finely refined pigment (PR254M).

[0523] [Manufacturing Examples 2-2 to 2-14]

[0524] In the above manufacturing example 2-1, except that the pigment used was changed from Pigment Red 254 to the pigments shown in the table below, the same processing as in the above manufacturing example 2-1 was performed to obtain each micronized pigment.

[0525] [Table 1]

[0526]

[0527] [Chemical Formula 39]

[0528]

[0529] <Preparation of Pigment Dispersion>

[0530] [Manufacturing Examples 3-1 to 3-19]

[0531] After mixing the materials listed in the table below, zirconia beads with a diameter of 0.5 mm were used, and the mixture was dispersed for 3 hours using an EIGER mill (EIGER Japan "Mini Model M-250 MKII"). The resulting mixture was then filtered through a 5.0 μm pore size filter to prepare a pigment dispersion.

[0532] [Table 2]

[0533]

[0534] (Micronized pigments)

[0535] PR254M, PR272M, PY139M, PY150M, PY185M, PG59M, PG58M, PG36M, PG7M, PB15:6M, PB15:4M, PB15:6M, PV23M, PPB001M, SQ001M: The micronized pigments manufactured in the manufacturing examples 2-1 to 2-14 above.

[0536] TiB: Titanium oxynitride particles (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0537] CB: Carbon black particles (manufactured by Cabot Corporation, average first-order particle size 15nm)

[0538] ZrO2: Zirconia particles (manufactured by Nippon Denko Co., Ltd., average first-order particle size 20nm)

[0539] TiO2: Titanium oxide particles (manufactured by ISHIHARA SANGYO KAISHA, LTD., Ltd., TTO-51(C), average primary particle size 10-30 nm, surface treated with alumina and stearic acid)

[0540] (derivative)

[0541] Derivatives 1-4: Compounds with the following structures

[0542] [Chemical Formula 40]

[0543]

[0544] (Resin solution)

[0545] B-3 to B-5: Resin solutions (B-3) to (B-5) manufactured in the above-described manufacturing examples 1-3 to 1-5.

[0546] (solvent)

[0547] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0548] <Preparation of Photocurable Compositions>

[0549] The raw materials listed in the table below were stirred and mixed until homogeneous, and then filtered through a filter with a pore size of 1 μm to produce a photocurable composition.

[0550] [Table 3]

[0551]

[0552] [Table 4]

[0553]

[0554] [Table 5]

[0555]

[0556] In the table above, the abbreviations for various materials represent the following:

[0557] (Pigment dispersion)

[0558] DisR01, DisR02, DisY01, DisY02, DisY03, DisG01, DisG02, DisG03, DisG04, DisB01, DisB02, DisB03, DisV01, DisIR01, DisIR02, DisK01, DisK02, DisW01, DisW02: Pigment dispersions manufactured in manufacturing examples 3-1 to 3-19 above.

[0559] (dye)

[0560] DyeM01: A dye with the following structure (weight-average molecular weight 10400, acid value 69 mg KOH / g, m: 4, n: 2).

[0561] [Chemical Formula 41]

[0562]

[0563] DyeB01: A dye with the following structure (weight average molecular weight 30,000).

[0564] [Chemical Formula 42]

[0565]

[0566] DyeIR01: A dye with the following structure

[0567] [Chemical Formula 43]

[0568]

[0569] (Resin solution)

[0570] B-1~B-2: Resin solutions (B-1)~(B-2) manufactured in manufacturing examples 1-1~1-2 above.

[0571] (Specific compound)

[0572] Compounds with the following structures

[0573] [Chemical Formula 44]

[0574]

[0575] (polymeric compounds)

[0576] 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% to 63% by mass).

[0577] M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide modified pentaerythritol tetraacrylate)

[0578] M-3: ARONIX M-510 (manufactured by TOAGOSEI CO.,LTD., a polyacid-modified acrylic oligomer)

[0579] (Photopolymerization initiator)

[0580] I-1: Compounds with the following structures

[0581] [Chemical Formula 45]

[0582]

[0583] I-2: ADEKA ARKLSNCI-730 (manufactured by ADEKA CORPORATION)

[0584] I-3: Compounds with the following structures

[0585] [Chemical Formula 46]

[0586]

[0587] (UV absorber)

[0588] U-1: Uvinul3050 (manufactured by BASF, benzophenone compound)

[0589] U-2: ADEKA STAB LA-F70 (manufactured by ADEKA CORPORATION, triazine compound)

[0590] U-3: ADEKA STAB LA-31RG (manufactured by ADEKA CORPORATION, benzotriazole compound)

[0591] (Polymerization inhibitor)

[0592] IN-1: p-Methoxyphenol

[0593] IN-2: 2,2,6,6-Tetramethylpiperidine 1-oxy radical

[0594] IN-3: ADEKA STAB AO-80 (manufactured by ADEKA CORPORATION)

[0595] (surfactant)

[0596] W-1: Compounds with the following structure (silicone surfactants, number-average molecular weight 1800)

[0597] [Chemical Formula 47]

[0598]

[0599] W-2: Megafac F-781F (manufactured by DIC Corporation, fluorinated surfactant)

[0600] (Quaternary ammonium salt compounds)

[0601] AN-1: Compounds with the following structure

[0602] [Chemical Formula 48]

[0603]

[0604] AN-2: Tetrabutylammonium bromide

[0605] AN-3: (CH3)3N + CH2CO2 -

[0606] (solvent)

[0607] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0608] S-2: 1-Methoxy-2-propanol (PGME)

[0609] S-3: Cyclopentanone

[0610] <Evaluation of Fit>

[0611] Each photocurable composition was spin-coated onto an 8-inch (1 inch is 2.54 cm) silicon wafer sprayed with hexamethyldisilazane to achieve a film thickness of 0.8 μm, and then heated at 100°C for 2 minutes. Next, a KrF scanning exposure machine was used, through a mask with an island pattern of 1.1 μm square, at an illumination of 35000 W / m². 2 Exposure 200mJ / cm 2 It was irradiated with KrF rays.

[0612] Next, a 0.3% by weight aqueous solution of tetramethylamine hydroxide (TMAH) was used for 40 seconds of swirling immersion development at 25°C. After rinsing with running water for 30 seconds, the mixture was spray-dried to form a pattern (pixels).

[0613] The obtained pixels were observed from above using a scanning electron microscope (manufactured by Hitachi, Ltd., S-9220), and the pattern size of the pixels was measured. Furthermore, the fit was evaluated using an optical microscope. The pattern size of all pixels at the point of fit was evaluated in five stages according to the following evaluation criteria.

[0614] -Evaluation Criteria-

[0615] A: The pattern size is greater than 0.9μm and less than 1.0μm, and all pixels are closely matched.

[0616] B: The pattern size is greater than 1.0μm and less than 1.05μm, and all pixels are closely aligned.

[0617] C: The pattern size is greater than 1.05μm and less than 1.1μm, and all pixels are closely matched.

[0618] D: If the pattern size is less than 1.1μm, all pixels will not be aligned.

[0619] <Evaluation of solvent resistance>

[0620] A substrate-forming composition (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater to achieve a post-baking thickness of 0.1 μm. The wafer was then heated at 220°C for 300 seconds using a hot plate to form the substrate layer, thus obtaining a silicon wafer (support) with the substrate layer. Next, various photocurable compositions were applied using spin coating to achieve a post-baking film thickness of 0.5 μm. This was then heated at 100°C for 2 minutes using a hot plate. Finally, the resulting composition layer was exposed to an illuminance of 35000 W / m² using a KrF scanning exposure machine. 2 Exposure 200mJ / cm 2 Exposure was performed using light with a wavelength of 248 nm (KrF rays). Next, the silicon wafer with the exposed coating was placed on a horizontal rotating stage of a spin / spray developer (DW-30 type, manufactured by CHEMITRONICS CO.,LTD.), and subjected to a 60-second spin-dip immersion treatment at 23°C using a 60% diluted solution of CD-2000 (manufactured by FUJIFILM Electronic Materials Co.,Ltd.). Then, the silicon wafer was fixed to the horizontal rotating stage using a vacuum chuck, and while rotating at 50 rpm, it was rinsed with pure water sprayed from above the center of rotation through a nozzle. Spray drying followed. Finally, a heat treatment (post-baking) was performed at 200°C for 300 seconds to form the film.

[0621] The spectrum of the membrane obtained above in the wavelength range of 400–1100 nm was measured using a UV-1800 spectrophotometer manufactured by SHIMADZU CORPORATION (spectrum A). After immersing the membrane in N-methylpyrrolidone for 30 minutes, it was washed with deionized water and 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. The maximum value of ΔAbs in the wavelength range of 400–1100 nm (ΔAbs_max) was used as an indicator of solvent resistance. The closer the value of ΔAbs_max is to 0, the better the solvent resistance.

[0622] -Evaluation Criteria-

[0623] A: ΔAbs_max is less than 0.1

[0624] B: ΔAbs_max is greater than 0.1 and less than 0.2.

[0625] C: ΔAbs_max is greater than 0.2 and less than 0.3.

[0626] D: ΔAbs_max is 0.3 or higher.

[0627] <Evaluation of Rectangularity>

[0628] A substrate-forming composition (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater to achieve a post-baking thickness of 0.1 μm. The wafer was then heated at 220°C for 300 seconds using a hot plate to form the substrate layer, thus obtaining a silicon wafer (support) with the substrate layer. Next, various photocurable compositions were applied using spin coating to achieve a post-baking film thickness of 0.5 μm. This was then heated at 100°C for 2 minutes using a hot plate. Finally, the obtained composition layer was exposed to 35000 W / m² illumination through a KrF scanning lithography machine, using a mask with a 0.5 μm square pattern. 2 Exposure 200mJ / cm 2 Exposure was performed using light with a wavelength of 248 nm (KrF line). Next, the silicon wafer with the exposed coating was placed on the horizontal turntable of a spin / spray developer (DW-30 type, manufactured by CHEMITRONICS Co., Ltd.), and subjected to a 60% dilution of CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 23°C for 60 seconds of spin-dip development, thereby forming a pattern on the silicon wafer. The patterned silicon wafer was fixed to the horizontal turntable using a vacuum chuck, and while rotating at 50 rpm, pure water was sprayed from above the center of rotation through a nozzle for rinsing, followed by spray drying. Finally, a 300-second heat treatment (post-baking) at 200°C was performed to form the pattern (pixels).

[0629] The cross-section of the fabricated pixels was observed using a scanning electron microscope, the angle of the pixel sidewalls relative to the silicon wafer surface was measured, and the rectangularity was evaluated using the following evaluation criteria.

[0630] -Evaluation Criteria-

[0631] A: The angle of the pixel's sidewall is greater than 80° and less than 100°.

[0632] B: The angle of the pixel sidewall is 75° or higher and less than 80°, or 100° or higher and less than 105°.

[0633] C: The angle of the pixel sidewall is greater than 70° and less than 75°, or greater than 105° and less than 110°.

[0634] D: The angle of the pixel sidewall is less than 70°, or greater than 110°.

[0635] The evaluation results are recorded in the table below. Furthermore, in the table below, the content of a specific compound in the total solids composition of the photocurable composition is recorded in the "Content of Specific Compound" column.

[0636] [Table 6]

[0637]

[0638] As shown in the table above, the evaluation results of the adhesion and solvent resistance of the examples are superior compared to the comparative examples.

[0639] For the photocurable compositions used in Examples 1-30, the exposure light source was changed from KrF rays to i rays (wavelength 365nm), and the same evaluation of adhesion, solvent resistance, and rectangularity was performed, with the same results as for KrF exposure.

Claims

1. A photocurable composition comprising compound A, a resin, and a photopolymerization initiator, comprising at least one compound selected from formulas (A-1) to (A-6), a resin, and a photopolymerization initiator. The content of compound A in the total solids component of the photocurable composition is 0.005% to 2% by mass. In the formula, R a1 ~R a13 Each can be used to represent a hydrogen atom or a methyl group independently.

2. The photocurable composition according to claim 1, wherein, The compound A is selected from at least one of the following: 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 claim 1 or 2, further comprising a trifunctional to hexafunctional polymeric compound having a structure different from that of compound A and having 3 to 6 groups containing olefinic unsaturated bonds.

4. The photocurable composition according to claim 1 or 2, wherein, The resin includes resins having groups containing olefinic unsaturated bonds.

5. The photocurable composition according to claim 4, wherein, The resin having groups containing olefinic unsaturated bonds contains groups represented by any of formulas (b-1) to (b-3). In equation (b-1), * represents a bonding bond, R b1 R represents a hydrogen atom or a methyl group. b2 Indicates a hydrogen atom or an organic group. In equation (b-2), * represents a bonding bond, R b3 Indicates a hydrogen atom or a methyl group. In equation (b-3), * represents a bonding bond, R b4 R represents a hydrogen atom or a methyl group. b5 It represents a hydrogen atom or an organic group.

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

7. The photocurable composition according to claim 1 or 2, further comprising a compound having a quaternary ammonium cation.

8. A film obtained using the photocurable composition according to claim 1 or 2.

9. A filter having the membrane of claim 8.

10. A solid-state imaging element having the membrane of claim 8.

11. An image display device having the membrane of claim 8.

Images