Photosensitive composition, method for producing photosensitive composition, cured film, color filter, light-shielding film, optical element, solid-state imaging element, headlight unit

Abstract

To provide a photosensitive composition that is superior in residue inhibition upon pattern formation and adhesion of the pattern to a base material, as well as superior in storage stability, and a method for producing a photosensitive composition, a cured film, a color filter, a light blocking film, an optical element, a solid state image sensor and a head light unit.SOLUTION: A photosensitive composition contains a black pigment, a resin with a graft chain and a carbon-carbon double bond, an acid compound with two or more carboxy groups, and a polymerizable compound. The acid compound has a molecular weight of 50.0-550.0, and the content of the acid compound is 0.3-5.0 mass% relative to the total solid content of the photosensitive composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a method for producing a photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit. [Background technology]

[0002] Color filters used in liquid crystal display devices are provided with a light-shielding film called a black matrix for the purpose of blocking light between colored pixels and improving contrast. Furthermore, currently, small and thin imaging units are installed in portable electronic devices such as mobile phones and PDAs (Personal Digital Assistants). Solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors are provided with a light-shielding film for the purposes of preventing noise generation and improving image quality.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition that can obtain high resolution and form a pattern with a high refractive index and high transmittance, and that includes "a dispersion composition containing titanium dioxide particles (A) having an average particle size of 1 nm to 100 nm, a graft copolymer (B) having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000, and a solvent (C), a polymerizable compound (D), and a polymerization initiator (E)." [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-127096 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, there has been a demand for increasing the pigment concentration in order to improve the optical properties required of light-shielding films. On the other hand, the present inventors have found that when the pigment concentration is increased based on the photosensitive resin composition described in Patent Document 1, it is difficult to simultaneously suppress residues when forming a pattern using the photosensitive resin composition and ensure adhesion of the formed pattern to a substrate. Furthermore, in general, photosensitive compositions are required to be free from pigment sedimentation, that is, to have excellent storage stability.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition that is excellent in the ability to suppress residues when a pattern is formed, the adhesion of the pattern to a substrate, and also has excellent storage stability. Another object of the present invention is to provide a method for producing a photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging element, and a headlight unit. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0008] (1) a black pigment; a resin having a graft chain and a carbon-carbon double bond; an acid compound having two or more carboxy groups; A photosensitive composition comprising a polymerizable compound, The molecular weight of the acid compound is 50.0 to 550.0, A photosensitive composition, wherein the content of the acid compound is 0.3 to 5.0% by mass based on the total solid content of the photosensitive composition. (2) The photosensitive composition according to (1), wherein the acid compound is an aliphatic carboxylic acid. (3) The photosensitive composition according to (1) or (2), wherein the acid compound has two or three carboxy groups. (4) The photosensitive composition according to any one of (1) to (3), wherein the acid compound has a pKa of 0.00 to 6.00. (5) The photosensitive composition according to any one of (1) to (4), wherein the acid compound has 1 to 34 carbon atoms. (6) The photosensitive composition according to any one of (1) to (5), wherein the content of the acid compound is 0.8 to 2.0% by mass based on the total solid content of the photosensitive composition. (7) The photosensitive composition according to any one of (1) to (6), wherein the mass ratio of the acid compound content to the resin content is 2 / 98 to 15 / 85. (8) The photosensitive composition according to any one of (1) to (7), wherein the graft chain has a polyester structure. (9) The photosensitive composition according to any one of (1) to (8), which contains two or more acid compounds. (10) The photosensitive composition according to any one of (1) to (9), further comprising a photopolymerization initiator. (11) A method for producing the photosensitive composition according to any one of (1) to (10), comprising the steps of: Step 1: Mixing a pre-mixture containing a black pigment, a resin, and an acid compound in a bead mill to obtain a mixture; The method for producing a photosensitive composition includes a step 2 of mixing the mixture with a polymerizable compound to obtain a photosensitive composition. (12) A cured film formed using the photosensitive composition according to any one of (1) to (10). (13) A color filter comprising the cured film according to (12). (14) A light-shielding film comprising the cured film according to (12). (15) An optical element comprising the cured film according to (12). (16) A solid-state imaging device comprising the cured film according to (12). (17) A headlight unit for a vehicle lamp, A light source and a light blocking portion that blocks at least a portion of the light emitted from the light source; A headlight unit, wherein the light-shielding part comprises the cured film according to (12). [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive composition which is excellent in the ability to suppress residues when a pattern is formed, the adhesion of the pattern to a substrate, and also has excellent storage stability. The present invention also provides a method for producing a photosensitive composition, a cured film, a color filter, a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0011] In this specification, the "solid content" of a composition refers to the components that form a cured film, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a cured film are also considered to be solid content.

[0012] Furthermore, in the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups that do not contain a substituent and groups that contain a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that do not contain a substituent (unsubstituted alkyl groups) but also alkyl groups that contain a substituent (substituted alkyl groups). In addition, in this specification, an organic group is a group containing at least one carbon atom.

[0013] Furthermore, in this specification, "actinic rays" or "radiation" refers to, for example, far ultraviolet rays, extreme ultraviolet (EUV: Extreme ultraviolet lithography), X-rays, electron beams, etc. Furthermore, in this specification, "light" refers to actinic rays and radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also writing with particle beams such as electron beams and ion beams.

[0014] In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. In this specification, "(meth)acrylic" means acrylic and methacrylic. In this specification, "(meth)acryloyl" means acryloyl and methacryloyl. In this specification, "monomer" and "monomer" have the same meaning.

[0015] In this specification, "ppm" means "parts-per-million (10 -6 ) and "ppb" stands for "parts-per-billion (10 -9 ) and "ppt" stands for "parts-per-trillion (10 -12 )"

[0016] In addition, the "weight average molecular weight (Mw)" in this specification is a polystyrene equivalent value determined by GPC (Gel Permeation Chromatography) method. The term "GPC method" as used herein refers to a method using a HLC-8020GPC (manufactured by Tosoh Corporation) as a measuring instrument, TSKgel SuperHZM-H, TSKgel SuperHZ4000, or TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) as a column, and THF (tetrahydrofuran) as an eluent.

[0017] The bonding direction of a divalent group (e.g., -COO-) represented in this specification is not limited unless otherwise specified. For example, when Y in a compound represented by the formula "XYZ" is -COO-, the compound may be "XO-CO-Z" or "X-CO-OZ".

[0018] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0019] [Photosensitive composition] The photosensitive composition of the present invention (hereinafter also referred to simply as "composition") is a photosensitive composition containing a black pigment, a resin having a graft chain and a carbon-carbon double bond (hereinafter also referred to as "specific resin"), an acid compound having two or more carboxy groups, and a polymerizable compound, wherein the molecular weight of the acid compound is 50.0 to 550.0, and the content of the acid compound is 0.3 to 5.0 mass% based on the total solid content of the photosensitive composition. The mechanism by which the problem of the present invention is solved when the composition having the above configuration is used is not entirely clear, but the present inventors speculate as follows. Increasing the content of black pigment in the composition in order to enhance the light-blocking properties of a cured film formed using the composition poses a problem in that the pigment in unexposed areas is not removed during development and remains. One common method for suppressing such residues is to increase the content of acid in the composition. However, this method also increases the acidity of the exposed areas of the cured film, thereby improving affinity with the developer, resulting in a new problem of reduced adhesion of the pattern to the substrate. In other words, adopting this method makes it difficult to achieve both the residue suppression and the pattern adhesion to the substrate, which are the objectives of the present invention. Furthermore, increasing the content of black pigment also leads to a decrease in the storage stability of the composition. On the other hand, in the composition of the present invention, first, the acid compound has two or more carboxy groups and has a molecular weight within a predetermined range, so that some of the carboxy groups in the molecule are adsorbed to the surface of the black pigment, while the carboxy groups that are not adsorbed are present in a form that covers the surface of the black pigment. This makes the surface of the black pigment acidic, which is thought to improve its affinity with an alkaline developer and thereby improve residue suppression. Furthermore, as described above, the acid compound is adsorbed onto the surface of the black pigment, which makes the black pigment particles more likely to repel each other, preventing sedimentation due to aggregation and improving storage stability. Furthermore, since the specific resin in the composition has a carbon-carbon double bond, it reacts with the polymerizable compound during exposure to form a strong film with improved crosslinking density, which is thought to give the exposed area excellent resistance to the developer and maintain adhesion of the pattern to the substrate. Hereinafter, the achievement of at least one of the effects of being better in suppressing residue when a pattern is formed using the composition, being better in adhesion of the pattern to the substrate, and being better in storage stability of the composition is also referred to as "the effect of the present invention being better." The components contained in the composition of the present invention will be described below.

[0020] [Black pigment] The composition of the present invention includes a black pigment. In this specification, the black pigment means a pigment that has absorption over the entire wavelength range of 400 to 700 nm, and for example, a black pigment that meets the evaluation criterion Z described below is preferred. First, a composition containing a black pigment, a transparent resin matrix (e.g., acrylic resin), and a solvent is prepared, with the black pigment content being 60% by mass relative to the total solids content. The resulting composition is applied to a glass substrate so that the thickness of the cured film after drying is 1 μm, forming a cured film. The light-blocking properties of the cured film after drying are evaluated using a spectrophotometer (e.g., Hitachi UV-3600). If the maximum transmittance of the cured film after drying at wavelengths of 400 to 700 nm is less than 10%, the black pigment is determined to meet evaluation standard Z. In evaluation standard Z, the maximum transmittance of the cured film after drying at wavelengths of 400 to 700 nm is more preferably less than 8%, and even more preferably less than 5%.

[0021] The black pigment may be prepared by combining a plurality of pigments that cannot be used alone to produce a black pigment, and adjusting the total to produce a black pigment. For example, a combination of pigments that have a color other than black when used alone may be used as the black pigment.

[0022] The average particle size of the black pigment is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less.From the viewpoint of better handleability, the average particle size is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 20 nm or more.

[0023] The average particle size is calculated by the following method. The composition of the present invention is diluted with propylene glycol monomethyl ether acetate (PGMEA) to prepare a measurement solution with a solids concentration of 0.2% by mass. Next, using a dynamic light scattering particle size distribution analyzer (LB-500 (product name) manufactured by Horiba, Ltd.) conforming to JIS8826:2005, data from the measurement solution is collected 50 times at 25°C using a 2 ml quartz measurement cell, and the number-based particle sizes obtained are arithmetically averaged to obtain the average particle size. Although the measurement solution was prepared using the composition of the present invention in the above, the measurement may also be performed using a colorant dispersion in which a black pigment is dispersed. For example, when the composition of the present invention contains particles other than the black pigment, the average particle size of the black pigment may be measured using a colorant dispersion in which the black pigment used in preparing the composition of the present invention is dispersed. Furthermore, when the composition of the present invention contains particles other than the black pigment, the average particle size of the black pigment may be measured after separating the black pigment from the other particles by any method.

[0024] The black pigment is preferably a pigment that can express a black color by itself, or a black pigment that can express a black color by itself and absorbs infrared rays may be used. Here, the black pigment that absorbs infrared rays has absorption in the infrared wavelength region (preferably, wavelengths of 650 to 1300 nm). Black pigments having a maximum absorption wavelength in the wavelength region of 675 to 900 nm are also preferred.

[0025] As the black pigment, various known black pigments can be used, and the black pigment may be an inorganic pigment or an organic pigment. The black pigment is preferably an inorganic pigment, since the light-shielding film has better light resistance. Among these, the black pigment is preferably one or more selected from the group consisting of titanium black, carbon black, and bisbenzofuranone compounds.

[0026] <Inorganic pigments> The inorganic pigment used as the black pigment is not particularly limited as long as it has light-shielding properties and is a particle containing an inorganic compound, and any known inorganic pigment can be used.

[0027] Examples of inorganic pigments include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Among these, metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe) are preferred. In other words, the inorganic pigment may contain two or more metal atoms. The above metal oxides, metal nitrides, and metal oxynitrides may be particles containing other metal atoms. For example, metal nitride-containing particles containing atoms selected from the elements of Groups 13 to 17 of the Periodic Table (preferably oxygen atoms and / or sulfur atoms) may be used. The above metal oxides, metal nitrides and metal oxynitrides may be coated with an inorganic and / or organic substance. Examples of the inorganic substance include metal atoms contained in the inorganic pigment. The organic substance may be an organic substance having a hydrophobic group, and a silane compound is preferred.

[0028] The method for producing the metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as it can produce a black pigment having the desired physical properties, and known production methods such as a gas phase reaction method can be used. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferred because it reduces the inclusion of impurities, easily produces particles with a uniform diameter, and has high productivity. The metal nitrides, metal oxides, or metal oxynitrides may be surface-modified. For example, they may be surface-modified with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0029] Among these, nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are more preferred, and zirconium nitride or oxynitride, or titanium nitride or oxynitride (titanium black) are even more preferred, in terms of being able to suppress the occurrence of undercuts when forming a light-shielding film.

[0030] Titanium black is a black particle containing titanium oxynitride. The surface of titanium black can be modified as necessary to improve dispersibility, suppress aggregation, etc. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a water-repellent substance as described in JP 2007-302836 A.

[0031] Methods for producing titanium black include a method in which a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open Publication No. 49-05432), a method in which ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride is reduced in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open Publication No. 57-205322), a method in which titanium dioxide or titanium hydroxide is reduced at high temperatures in the presence of ammonia (Japanese Patent Laid-Open Publication Nos. 60-065069 and 61-201610), and a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and then reduced at high temperatures in the presence of ammonia (Japanese Patent Laid-Open Publication No. 61-201610).

[0032] The particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm. The specific surface area of ​​titanium black is not particularly limited, but in order to achieve a predetermined water repellency after surface treatment with a water repellent agent, the value measured by the BET (Brunauer, Emmett, Teller) method should be 5 to 150 m. 2 / g, and 20 to 100m 2 / g is more preferred.

[0033] Examples of titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), and MT-150A (trade name, manufactured by Teika Corporation).

[0034] The composition also preferably contains titanium black as a dispersed substance containing titanium black and Si atoms. In this embodiment, titanium black is contained as a dispersed substance in the composition. The ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed substance is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, calculated by mass. Here, the dispersed substance includes both titanium black in the form of primary particles and in the form of aggregates (secondary particles). Furthermore, if the Si / Ti of the dispersed substance is a predetermined value or more, when a composition layer using the dispersed substance is patterned by photolithography or the like, residues are less likely to remain in the removed area, and if the Si / Ti of the dispersed substance is a predetermined value or less, the light-blocking ability is likely to be good.

[0035] The following methods can be used to change the Si / Ti ratio of the dispersed material (for example, to 0.05 or more). First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this mixture is then reduced at a high temperature (for example, 850 to 1000°C) to obtain a dispersed material containing titanium black particles as the main component and Si and Ti. Titanium black with an adjusted Si / Ti ratio can be produced, for example, by the method described in paragraphs

[0005] and

[0016] to

[0021] of JP 2008-266045 A. The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed substance can be measured, for example, by the method (2-1) or the method (2-3) described in paragraphs

[0054] to

[0056] of WO 2011 / 049090.

[0036] In the dispersed substance containing titanium black and Si atoms, the titanium black described above can be used. Furthermore, in this dispersed substance, in order to adjust dispersibility, colorability, etc., one or more of the following black pigments may be used in combination with titanium black: composite oxides of multiple metals selected from Cu, Fe, Mn, V, Ni, etc.; cobalt oxide; iron oxide; carbon black; and aniline black. In this case, it is preferable that the dispersed substance made of titanium black accounts for 50% by mass or more of the total dispersed substance.

[0037] Inorganic pigments also include carbon black. Carbon black includes, for example, furnace black, channel black, thermal black, acetylene black, and lamp black. As the carbon black, carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used. Examples of commercially available carbon black include inorganic pigments such as CI Pigment Black 7.

[0038] The carbon black is preferably surface-treated. The surface treatment can modify the surface condition of the carbon black particles and improve the dispersion stability in the composition. Examples of surface treatments include coating with a resin, surface treatment to introduce acidic groups, and surface treatment with a silane coupling agent.

[0039] The carbon black is preferably carbon black that has been coated with a resin. By coating the surface of carbon black particles with an insulating resin, the light-shielding and insulating properties of the light-shielding film can be improved. Furthermore, the reliability of the image display device can be improved by reducing leakage current, etc. Therefore, this is suitable for use in applications where the light-shielding film requires insulation. Examples of the coating resin include epoxy resin, polyamide, polyamideimide, novolac resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide. The content of the coating resin is preferably 0.1 to 40 mass %, more preferably 0.5 to 30 mass %, based on the total amount of carbon black and coating resin, in order to provide a light-shielding film with better light-shielding and insulating properties.

[0040] Examples of inorganic pigments used as black pigments include zirconium described in JP 2017-222559 A, WO 2019 / 130772 A, WO 2019 / 059359 A, and JP 2009-091205 A, the contents of which are incorporated herein by reference.

[0041] <Organic pigments> The organic pigment used as the black pigment is not particularly limited as long as it has light-shielding properties and is a particle containing an organic compound, and known organic pigments can be used. In the present invention, examples of organic pigments include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds or perylene compounds are preferred.

[0042] Examples of the bisbenzofuranone compound include the compounds described in JP-A Nos. 2010-534726, 2012-515233, and 2012-515234. The bisbenzofuranone compound is available as "Irgaphor Black" (trade name) manufactured by BASF. Examples of perylene compounds include those described in JP-A-62-001753 and JP-B-63-026784. Perylene compounds are available as CI Pigment Black 21, 30, 31, 32, 33, and 34.

[0043] The content of the black pigment is preferably from 10 to 90 mass %, more preferably from 25 to 80 mass %, and even more preferably from 45 to 70 mass %, based on the total solid content of the composition. The composition may contain only one type of black pigment, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0044] [Specific resin] The composition of the present invention contains a resin (specific resin) having a graft chain and a carbon-carbon double bond. The specific resin can function as a dispersant for the black pigment and as a binder in the cured film. The graft chain of the specific resin means a polymer chain that branches off from the main chain and extends. The polymer chain has a plurality of repeating units. The length of the graft chain is not particularly limited, but as the graft chain becomes longer, the steric repulsion effect becomes stronger, thereby improving the dispersibility of the black pigment. In the graft chain, the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500.

[0045] The graft chain is preferably a polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, and more preferably a polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic structure. The polyester structure includes a polycaprolactone structure and a polyvalerolactone structure. The polycaprolactone structure refers to a structure containing a ring-opened ε-caprolactone structure as a repeating unit, and the polyvalerolactone structure refers to a structure containing a ring-opened δ-valerolactone structure as a repeating unit.

[0046] The carbon-carbon double bond is not particularly limited, but examples thereof include ethylenically unsaturated bonds. The specific resin preferably has a group having a carbon-carbon double bond, and more preferably has a functional group having an ethylenically unsaturated bond, such as a (meth)acryloyl group, a vinyl group, or a styryl group. The carbon-carbon double bond equivalent of the specific resin is preferably 0.05 to 1.50 mmol / g. The lower limit is more preferably 0.10 mmol / g or more, and even more preferably 0.30 mmol / g or more. The upper limit is more preferably 1.00 mmol / g or less, and even more preferably 0.80 mmol / g or less.

[0047] In the specific resin, the graft chain and the carbon-carbon double bond may be contained in the same repeating unit, or the graft chain and the carbon-carbon double bond may be contained in different repeating units. When the graft chain and the carbon-carbon double bond are contained in the same repeating unit, the group having the carbon-carbon double bond is preferably located on the terminal side of the graft chain. When the graft chain and the carbon-carbon double bond are contained in different repeating units, an embodiment in which the specific resin contains a repeating unit that has a graft chain but no carbon-carbon double bond, and a repeating unit that has a carbon-carbon double bond but no graft chain, is given.

[0048] The specific resin preferably contains the repeating unit having the carbon-carbon double bond and the graft chain (hereinafter simply referred to as "repeating unit 1"). In particular, the specific resin more preferably contains a repeating unit represented by any one of formulas (1) to (4), and even more preferably contains a repeating unit represented by formula (1).

[0049] [ka]

[0050] [ka]

[0051] In equations (1) to (4), Q 1 is a group represented by any one of formulas (QX1), (QNA), and (QNB), and Q 2 is a group represented by any one of formulas (QX2), (QNA), and (QNB), and Q 3 is a group represented by any one of formulas (QX3), (QNA), and (QNB), and Q 4 is a group represented by any one of formula (QX4), formula (QNA), and formula (QNB). In the formulae (QX1) to (QX4), (QNA), and (QNB), *a represents the bonding position on the main chain side, and *b represents the bonding position on the side chain side. In equations (1) to (4), W 1 ~W 4 each independently represents a single bond, an oxygen atom, or NH. In formulas (QX1) to (QX4) and (4), X 1 ~X 5each independently represents a hydrogen atom or a monovalent organic group; X 1 ~X 5 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0052] In formulas (1) to (4), Y 1 ~Y 4 each independently represents a single bond or a divalent linking group, and examples of the divalent linking group include linking groups represented by formulae (Y-1) to (Y-23).

[0053] [ka]

[0054] In formulas (Y-1) to (Y-23), A is W in formulas (1) to (4). 1 ~W 4 B represents the bonding position with either of the W 1 ~W 4 represents the bonding position to the group on the opposite side to either of the groups.

[0055] In formulas (1) to (4), Z 1 ~Z 4 each independently represents a group having a carbon-carbon double bond. The group having a carbon-carbon double bond is preferably a group represented by formula (W1) or a group represented by formula (W2).

[0056] [ka]

[0057] In formula (W1) and formula (W2), * represents a bonding position. L in formula (W1) W1 and L in formula (W2) W2 each independently represents a single bond or a divalent linking group. Divalent linking groups include ether groups (-O-), carbonyl groups (-CO-), ester groups (-COO-), thioether groups (-S-), -SO2-, and -NR N -(R N represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group which may have a substituent (an alkylene group, an alkenylene group (e.g., -CH=CH-), an alkynylene group (e.g., -C≡C-, etc.), and an arylene group), -SiR SX 2-(R SX represents a hydrogen atom or a substituent, and groups formed by combining these groups. The number of carbon atoms in the divalent hydrocarbon group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Examples of the substituent that the divalent hydrocarbon group may have include a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, and an amino group. Examples of the group formed by combining the above divalent hydrocarbon groups include -(O) m1 -Optionally substituted divalent hydrocarbon group-(O-optionally substituted divalent hydrocarbon group) n1 -O- is exemplified. m1 represents 0 or 1. n1 represents an integer of 0 to 5, preferably 1 or 2.

[0058] Formula (W2) is a group having an onium salt structure, O - (oxygen anion) and N + An ionic bond is formed between the cation and the quaternized nitrogen. In formula (W2), R W each independently represents an alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 15. In addition, the three R W Of these, one R W The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 to 15, more preferably 10 to 15, and the remaining two R W The alkyl group represented by the formula (I) preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0059] In formula (W1) and formula (W2), Z 5 represents a (meth)acryloyl group, a vinyl group, or a styryl group.

[0060] In formulas (1) to (4), n, m, p, and q each independently represent an integer of 2 to 500. Of these, an integer of 6 to 200 is more preferable. In formula (1) and formula (2), j and k each independently represent an integer of 2 to 8, preferably an integer of 4 to 6, more preferably 5, in that the effects of the present invention are more excellent.

[0061] In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. 3 may be the same or different from each other. In formula (4), R 4 represents a hydrogen atom or a monovalent organic group. The structure of the monovalent organic group is not particularly limited. 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. 4 When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms. 4 may be the same or different from each other.

[0062] The specific resin may contain repeating units represented by formulas (1) to (4) having structures different from each other. In formulas (1) and (2), j and k may have structures different from each other in the side chain. In formulas (3) and (4), a plurality of R 3 , R 4 , and X 5 may be the same or different from each other.

[0063] When the specific resin contains repeating unit 1 (for example, a repeating unit represented by the above formulas (1) to (4)), the content of repeating unit 1 is preferably 5 to 50 mol %, more preferably 10 to 40 mol %, based on the total repeating units of the specific resin.

[0064] The specific resin may contain repeating units other than the repeating unit 1 described above. Other repeating units include, for example, repeating units having a functional group capable of interacting with the black pigment. Examples of the functional group capable of interacting with the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group, and an acid group is preferred. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphate group. When the specific resin contains a repeating unit having a functional group capable of forming an interaction with the black pigment, the content of the repeating unit having a functional group capable of forming an interaction with the black pigment is preferably 5 to 80 mol %, and more preferably 30 to 70 mol %, based on the total repeating units of the specific resin.

[0065] The other repeating unit may be a repeating unit having a graft chain but no carbon-carbon double bond (hereinafter, simply referred to as "repeating unit 2"). The preferred range of the length of the graft chain in the repeating unit 2 is the same as the preferred range of the length of the graft chain in the repeating unit 1. The graft chain contained in repeating unit 2 is preferably a polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, and more preferably a polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic structure. The polyester structure includes a polycaprolactone structure and a polyvalerolactone structure.

[0066] The graft chain of repeating unit 2 does not contain a carbon-carbon double bond. The repeating unit 2 may have the above-mentioned functional group capable of forming an interaction with the black pigment. The acid group may be in a form including a part of the structure of the graft chain (for example, a —CO— group).

[0067] Examples of the repeating unit 2 include repeating units represented by the following formulas (1-1) to (4-1).

[0068] [ka]

[0069] Q in formula (1-1) 1 , W 1 , Y 1 The definitions of n and j are as follows: Q 1 , W 1 , Y 1 , n and j are defined as follows: Q in equation (2-1) 2 , W 2 , Y 2 The definitions of m and k are as follows: Q 2 , W 2 , Y 2 , m and k are defined as follows: Q in equation (3-1) 3 , W 3 , Y 3 , R 3 The definition of and p is Q in Eq. (1) 3 , W 3 , Y 3 , R 3 and the definition of p. Q in equation (4-1) 4 , W 4 , Y 4 , R 4 , X 5 The definition of and q is Q in Eq. (1) 4 , W 4 , Y 4 , R 4 , X 5 and q. That is, Z in formulas (1-1) to (4-1) 11 ~Z 14 The definitions of the symbols other than are the same as those of the respective groups in formulas (1) to (4). Z 11 ~Z 14 each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, or an amino group. The number of carbon atoms in the alkyl group and the alkyl moiety in the alkoxy group is not particularly limited, but is preferably 1 to 10. The alkyl group and the alkyl moiety in the alkoxy group may be linear or branched.

[0070] When the specific resin contains repeating unit 2 (for example, a repeating unit represented by any of the above formulas (1-1) to (4-1)), the content of repeating unit 2 is preferably 1 to 90 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 90 mol %, based on the total repeating units of the specific resin. In addition, the specific resin is Z 11 When the specific resin contains a repeating unit represented by formula (1-1) in which is an alkyl group or an alkoxy group, the total content of the repeating units represented by formula (1-1) may be 1 to 50 mol %, or may be 2 to 30 mol %, based on all repeating units of the specific resin.

[0071] As described above, it is also preferable that the specific resin includes a repeating unit that has a graft chain but no carbon-carbon double bond, and a repeating unit that has a carbon-carbon double bond but no graft chain. Examples of repeating units having a graft chain but no carbon-carbon double bond include repeating unit 2 above.

[0072] The weight average molecular weight (Mw) of the specific resin is preferably 2,500 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and even more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and even more preferably 5,000 or more.

[0073] The content of the specific resin is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, based on the total solid content of the composition, in terms of achieving better effects of the present invention. The composition may contain only one specific resin, or two or more specific resins. When two or more specific resins are contained, the total amount thereof is preferably within the above range.

[0074] [Acid compound] The composition of the present invention comprises an acid compound. The acid compound has two or more carboxy groups. The number of carboxy groups that the acid compound has is preferably 2 to 5, and more preferably 2 or 3, in terms of better effects of the present invention. The molecular weight of the acid compound is 50.0 to 550.0, and more preferably 100.0 to 450.0 in terms of better effects of the present invention. The number of carbon atoms in the acid compound is not particularly limited as long as it falls within the range that satisfies the above molecular weight, but is preferably 1 to 34, more preferably 2 to 30, and even more preferably 2 to 20, in terms of providing better effects for the present invention.

[0075] The pKa of the acid compound is not particularly limited, but is preferably from −3.00 to 8.00, more preferably from 0.00 to 6.00, still more preferably from 1.00 to 5.00, and particularly preferably from 3.00 to 5.00, in terms of better effects of the present invention. When the acid compound has a plurality of pKa values, it is preferable that the pKa value with the smallest value is within the above range.

[0076] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0077] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0078] The acid compound is preferably a compound represented by formula (A).

[0079] [ka]

[0080] In formula (A), L a represents an optionally substituted na-valent aliphatic hydrocarbon group or an optionally substituted na-valent aromatic ring group, where na represents an integer of 2 or greater. Among these, the effect of the present invention is more excellent, and L a As the acid compound, an optionally substituted Na-valent aliphatic hydrocarbon group is preferred. That is, as the acid compound, a divalent or higher aliphatic carboxylic acid is preferred.

[0081] An na-valent aliphatic hydrocarbon group is a group formed by removing na hydrogen atoms from an aliphatic hydrocarbon. The carbon number of the na-valent aliphatic hydrocarbon group is not particularly limited, but is preferably 2 to 32, and more preferably 2 to 20, in terms of providing better effects for the present invention. The na-valent aliphatic hydrocarbon group may be linear, branched or cyclic. The na-valent aliphatic hydrocarbon group may have an unsaturated bond in the molecule. If an unsaturated bond is present, it may be either a cis or trans isomer. When na is 2, the aliphatic hydrocarbon group represents a divalent aliphatic hydrocarbon group. The na-valent aliphatic hydrocarbon group may have a substituent. The number of the substituents is not particularly limited, and may be 1 or 2. Examples of the substituent that the na-valent aliphatic hydrocarbon group may have include a hydroxy group, a halogen atom, and an alkyloxycarbonyl group.

[0082] An na-valent aromatic ring group is a group formed by removing na hydrogen atoms from an aromatic ring. Examples of the na-valent aromatic ring group include a na-valent aromatic hydrocarbon ring group and a na-valent aromatic heterocyclic group, with a na-valent aromatic hydrocarbon ring group being preferred. The number of carbon atoms in the na-valent aromatic ring group is not particularly limited, but is preferably 4 to 32, and more preferably 5 to 20, in terms of providing better effects for the present invention. The aromatic ring constituting the na-valent aromatic ring group may be a single ring, a linked ring, or a condensed ring. The linked ring is a ring formed by linking multiple aromatic rings via single bonds, such as a biphenyl group. Examples of the aromatic hydrocarbon ring constituting the na-valent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, a phenanthrene ring, and a pyrene ring. Examples of the aromatic heterocycle constituting the na-valent aromatic heterocyclic group include a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiophene ring, an oxazole ring, and a thiazole ring. The aromatic hydrocarbon group having a valence of na may have a substituent. The number of the substituents is not particularly limited, and may be 1 or 2. Examples of the substituent that the sodium-valent aromatic hydrocarbon group may have include a hydroxy group, a halogen atom, an alkyl group, and an alkyloxycarbonyl group.

[0083] na is preferably 2 to 5, more preferably 2 or 3, in that the effects of the present invention are more excellent.

[0084] Examples of acid compounds having two carboxy groups include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, eicosadienedioic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, phthalic acid, terephthalic acid, isophthalic acid, 2,5-dichloroisophthalic acid, toluenedicarboxylic acid, sulfobenzenedicarboxylic acid, naphthalenedicarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid-2,3-dimethyl, octane-4,5-dicarboxylic acid, nonane-1,3-dicarboxylic acid, 2-butyloctanedioic acid, and pyrenedicarboxylic acid. Among these, malonic acid, succinic acid, maleic acid, and fumaric acid are preferred, with succinic acid being more preferred, in terms of achieving better effects of the present invention. Examples of acid compounds having three carboxy groups include trimellitic acid, citric acid, 1α,3α,5β-cyclohexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,4,5-naphthalenetricarboxylic acid, and 1-(1-propenyl) 3-butene-1,2,3-tricarboxylic acid. Examples of acid compounds having four carboxy groups include benzene-1,2,3,5-tetracarboxylic acid, butane-1,1,1,2-tetracarboxylic acid, butane-1,1,1,4-tetracarboxylic acid, butane-1,1,2,3-tetracarboxylic acid, 1,6,8,14-tetradecanetetracarboxylic acid, 1,3,5,7-naphthalenetetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,3,4,5-furantetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid. An example of an acid compound having five carboxy groups is benzenepentacarboxylic acid.

[0085] The content of the acid compound is preferably 0.3 to 5.0 mass %, more preferably 0.8 to 2.0 mass %, and even more preferably 0.8 to 1.5 mass %, based on the total solid content of the composition, in terms of achieving better effects of the present invention. The composition may contain one or more acid compounds, but preferably contains two or more, as this will provide better effects of the present invention. When two or more types are contained, the total amount thereof is preferably within the above range. The mass ratio of the content of the acid compound to the content of the specific resin is preferably from 2 / 98 to 30 / 70, and more preferably from 2 / 98 to 15 / 85, in terms of achieving better effects of the present invention.

[0086] [Polymerizable compound] The composition of the present invention contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to an organic compound (e.g., an organic compound containing an ethylenically unsaturated group) that can be polymerized by the action of a polymerization initiator or the like described below, and is a component separate from the specific resin described above. When the composition of the present invention contains a solvent, the polymerizable compound is preferably present in the form of a solution in the solvent.

[0087] The molecular weight of the polymerizable compound (weight average molecular weight when the polymerizable compound has a molecular weight distribution) is not particularly limited, but is preferably 2500 or less. The lower limit is preferably 100 or more.

[0088] The polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond). That is, the composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound. The number of ethylenically unsaturated bond groups contained in the polymerizable compound is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and particularly preferably 4 or more. The upper limit of the number of ethylenically unsaturated bond groups contained in the polymerizable compound is, for example, 15 or less. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

[0089] As the polymerizable compound, for example, the compounds described in paragraph

[0050] of JP-A No. 2008-260927 and paragraph

[0040] of JP-A No. 2015-068893 can be used, the contents of which are incorporated herein by reference.

[0090] The polymerizable compound may be in any chemical form, such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.

[0091] The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph

[0227] of JP-A No. 2013-029760 and paragraphs

[0254] to

[0257] of JP-A No. 2008-292970 can be used by reference, and the contents of these compounds are incorporated herein by reference.

[0092] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. and A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.), as well as compounds having a structure in which the (meth)acryloyl group is connected via an ethylene glycol residue or a propylene glycol residue (e.g., SR454 and SR499, both of which are commercially available from Sartomer). Oligomers of these compounds can also be used. Alternatively, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) may be used. Alternatively, the polymerizable compound may be a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond therein, such as KAYARAD DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.). Preferred embodiments of the polymerizable compound are shown below.

[0093] The polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and more preferably a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

[0094] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development solubility is good, and when it is 40 mgKOH / g or less, it is advantageous in terms of production and / or handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

[0095] In a preferred embodiment, the polymerizable compound is a compound containing a caprolactone structure. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0096] [ka]

[0097] In formula (Z-1), all of the six R's are groups represented by the following formula (Z-2), or 1 to 5 of the six R's are groups represented by the following formula (Z-2), and the remainder are groups represented by the following formula (Z-3).

[0098] [ka]

[0099] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents 1 or 2, and * represents the bonding position.

[0100] [ka]

[0101] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents the bonding position.

[0102] Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and include DPCA-20 (where m=1 in the above formulas (Z-1) to (Z-3), the number of groups represented by formula (Z-2)=2, and R 1 are all hydrogen atoms), DPCA-30 (same formula, m=1, number of groups represented by formula (Z-2)=3, R 1 are all hydrogen atoms), DPCA-60 (same formula, m=1, number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms) and DPCA-120 (in the formula, m=2, the number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms). In addition, an example of a commercially available polymerizable compound containing a caprolactone structure is M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

[0103] The polymerizable compound may also be a compound represented by the following formula (Z-4) or formula (Z-5).

[0104] [ka]

[0105] In formula (Z-4) and formula (Z-5), E is -((CH2) y CH2O)- or -((CH2) y CH(CH3)O)-, y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the sum of the m's is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer of 0 to 10, and the sum of all n's is an integer of 0 to 60.

[0106] In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of the m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12. In addition, -((CH2) y CH2O)- or -((CH2) y In the case of CH(CH3)O)-, the terminal on the oxygen atom side is preferably bonded to X.

[0107] The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), an embodiment in which all six Xs are acryloyl groups, and an embodiment in which all six Xs are acryloyl groups in formula (Z-5) are a mixture of a compound in which at least one of the six Xs is a hydrogen atom are preferred. Such a configuration can further improve developability.

[0108] The total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0109] The polymerizable compound may also contain a cardo skeleton. The polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton. Examples of polymerizable compounds containing a cardo skeleton include Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Oxol (manufactured by Osaka Gas Chemicals Co., Ltd.). The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. An example of such a polymerizable compound is NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). The content of ethylenically unsaturated groups in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more, and the upper limit is preferably 20.0 mmol / g or less.

[0110] The content of the polymerizable compound in the composition is preferably from 5 to 60% by mass, more preferably from 7 to 30% by mass, and more preferably from 10 to 20% by mass, based on the total solid content of the composition. The composition may contain only one type of polymerizable compound, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0111] The composition of the present invention may contain other components in addition to the black pigment, specific resin, acid compound, and polymerizable compound described above.

[0112] [Resins other than specified resins] The composition of the present invention may contain a resin other than the specific resin (hereinafter simply referred to as "other resin"). The other resin can function as a dispersant for the black pigment and as a binder in the cured film. Examples of other resins include (meth)acrylic resins, epoxy resins, enethiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and polyalkyleneimine resins (polyethyleneimine resins, etc.). One of these resins may be used alone, or two or more may be used in combination. As the cyclic olefin resin, norbornene resin is preferred from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds containing epoxy groups with other silicon compounds, and copolymers of polymerizable unsaturated compounds having epoxy groups with other polymerizable unsaturated compounds. Furthermore, as the epoxy resin, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer), etc. can also be used. The other resin may be a cardo resin, which has a cardo skeleton.

[0113] Other resins include alkali-soluble resins. The composition of the present invention contains an alkali-soluble resin, which can effectively suppress the generation of development residues during pattern formation. Examples of alkali-soluble resins include resins having an acid group. Examples of the acid group include a carboxy group, a phosphate group, a sulfonic acid group, and a phenolic hydroxy group, with a carboxy group being preferred. The alkali-soluble resin may have only one type of acid group, or two or more types.

[0114] The alkali-soluble resin preferably contains a repeating unit having an acid group. The content of the repeating units having an acid group is preferably 5 to 70 mol % based on the total repeating units of the alkali-soluble resin. The upper limit of the content of the repeating units having an acid group is preferably 50 mol % or less, more preferably 30 mol % or less. The lower limit of the content of the repeating units having an acid group is preferably 10 mol % or more, more preferably 20 mol % or more.

[0115] The alkali-soluble resin is also preferably an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth)allyl group (meaning both an allyl group and a methallyl group) and a (meth)acryloyl group. The alkali-soluble resin having a polymerizable group is preferably a resin containing a repeating unit having a polymerizable group and a repeating unit having an acid group.

[0116] The alkali-soluble resin also preferably contains a repeating unit derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

[0117] [ka]

[0118] In formula (ED1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[0119] [ka]

[0120] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description in JP-A-2010-168539, the contents of which are incorporated herein by reference.

[0121] Specific examples of ether dimers can be found in, for example, paragraph

[0317] of JP-A-2013-029760, the contents of which are incorporated herein by reference.

[0122] The alkali-soluble resin also preferably contains a repeating unit derived from a compound represented by the following formula (X).

[0123] [ka]

[0124] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n represents an integer of 1 to 15.

[0125] The alkali-soluble resin may be a cardo resin having a cardo skeleton, such as V-259ME (manufactured by Nippon Steel & Sumitomo Metal Corporation). For details of alkali-soluble resins, please refer to the descriptions in paragraphs

[0558] to

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

[0685] to

[0700] of the specification of U.S. Patent Application Publication No. 2012 / 0235099) and the descriptions in paragraphs

[0076] to

[0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference.

[0126] The acid value of the other resin (particularly, the alkali-soluble resin) is preferably 10 to 500 mgKOH / g. The lower limit is preferably 30 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, even more preferably 200 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. The ethylenically unsaturated bond equivalent (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the other resin by the molecular weight (g / mol) of the other resin) of the other resin (particularly, the alkali-soluble resin) is preferably 0.4 to 2.5 mmol / g. The lower limit is preferably 1.0 mmol / g or more, more preferably 1.2 mmol / g or more. The upper limit is preferably 2.3 mmol / g or less, more preferably 2.0 mmol / g or less. In particular, when the composition of the present invention contains a resin having an acid value of 10 to 100 mgKOH / g and an ethylenically unsaturated bond equivalent of 1.0 to 2.0 mmol / g, peeling after a humidity resistance test can be further suppressed.

[0127] Specific examples of alkali-soluble resins include resins having the following structures: In the following structural formulas, Me represents a methyl group.

[0128] [ka]

[0129] The composition of the present invention may contain a resin having a basic group (hereinafter, also simply referred to as a "basic resin"). Examples of the basic group include an amino group and an ammonium salt group. The basic resin may further have an acid group, and such a resin is also an alkali-soluble resin. The amine value of the resin having a basic group is preferably from 10 to 250 mgKOH / g, more preferably from 50 to 200 mgKOH / g.

[0130] The basic resin may be a resin having a tertiary amino group and a quaternary ammonium salt group, and is preferably a resin containing a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group. The basic resin more preferably has a block structure of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group. The resin having a tertiary amino group and a quaternary ammonium salt group preferably has an amine value of 10 to 250 mgKOH / g and a quaternary ammonium salt value of 10 to 90 mgKOH / g, more preferably an amine value of 50 to 200 mgKOH / g and a quaternary ammonium salt value of 10 to 50 mgKOH / g.The resin having a tertiary amino group and a quaternary ammonium salt group preferably has a weight average molecular weight (Mw) of 3,000 to 300,000, more preferably 5,000 to 30,000. Examples of resins having a tertiary amino group and a quaternary ammonium salt group include ethylenically unsaturated monomers having a tertiary amino group, ethylenically unsaturated monomers having a quaternary ammonium salt group, and copolymers of other ethylenically unsaturated monomers. Regarding the monomer, the disclosures of paragraphs

[0150] to

[0170] of International Publication No. 2018 / 230486 can be referred to, and the disclosures thereof are incorporated herein by reference. Furthermore, resins having acidic groups as described in paragraphs

[0079] to

[0160] of Japanese Patent Application Laid-Open No. 2018-087939 may also be used in combination.

[0131] The basic resin preferably contains a nitrogen atom in the main chain. The resin containing a nitrogen atom in the main chain (hereinafter also referred to as an oligoimine resin) preferably contains a graft chain having 40 to 10,000 atoms and a repeating unit having a functional group with a pKa of 14 or less. The oligoimine resin preferably contains at least one repeating unit selected from poly(lower alkyleneimine)-based (such as poly(ethyleneimine)-based), polyallylamine-based, polydiallylamine-based, metaxylenediamine-epichlorohydrin polycondensate-based, and polyvinylamine-based. For details of oligoimine-based resins, see paragraphs

[0102] to

[0166] of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[0132] The composition of the present invention preferably contains a resin as a dispersant (hereinafter also simply referred to as a "dispersant"). Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. When the total amount of the acid groups and the amount of the basic groups is taken as 100 mol%, the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more, and more preferably a resin consisting essentially of acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. A basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. A basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of acid groups and basic groups is 100 mol %. A resin having basic groups is preferred as the dispersant, and a basic dispersant is more preferred.

[0133] Examples of dispersants include the above-mentioned resins having a tertiary amino group and a quaternary ammonium salt group, and oligoimine resins.

[0134] The resin used as a dispersant is preferably a resin containing a repeating unit having an acid group. The resin used as a dispersant is also preferably a resin having a structure in which multiple polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs

[0196] to

[0209] of JP-A-2013-043962. The aforementioned alkali-soluble resins can also be used as dispersants.

[0135] It is also preferable to use the dispersant described in JP 2019-078878 A.

[0136] Examples of commercially available dispersants include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 20000, and Solsperse 76500 (manufactured by Lubrizol Japan).

[0137] The compositions of the present invention may also include a polyalkyleneimine. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred.

[0138] The molecular weight of the polyalkyleneimine is preferably at least 100, more preferably at least 200, and even more preferably at least 250. The upper limit is preferably at most 100,000, more preferably at most 50,000, even more preferably at most 10,000, and particularly preferably at most 2,000. Regarding the molecular weight value of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the polyalkyleneimine cannot be calculated from the structural formula or calculation is difficult, the value of the number average molecular weight measured by the boiling point elevation method is used. When the molecular weight cannot be measured by the boiling point elevation method or measurement is difficult, the value of the number average molecular weight measured by the viscosity method is used. When the molecular weight cannot be measured by the viscosity method or measurement by the viscosity method is difficult, the value of the number average molecular weight measured in polystyrene equivalent by GPC (gel permeation chromatography) method is used.

[0139] The amine value of the polyalkyleneimine is preferably 2.7 mmol / g or more, more preferably 5 mmol / g or more, even more preferably 10 mmol / g or more, and particularly preferably 15 mmol / g or more.

[0140] The polyalkyleneimine is preferably polyethyleneimine. The polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total amount of primary amino groups, secondary amino groups, and tertiary 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.).

[0141] The content of the other resin in the composition is preferably from 10 to 50 mass %, more preferably from 15 to 40 mass %, and even more preferably from 20 to 35 mass %, based on the total solid content of the composition. The composition may contain only one type of other resin, or two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0142] [Polymerization initiator] The composition of the present invention may contain a polymerization initiator. As the polymerization initiator, for example, a known polymerization initiator can be used, such as a photopolymerization initiator or a thermal polymerization initiator, with a photopolymerization initiator being preferred.

[0143] Examples of the thermal polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl-(2,2')-azobis(2-methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate. Examples of the thermal polymerization initiator include those described on pages 65 to 148 of "Ultraviolet Curing System" by Kato Kiyomi (published by Sogo Gijutsu Center Co., Ltd., 1989).

[0144] The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet to visible light range is preferred. As the photopolymerization initiator, a photoradical polymerization initiator is preferred.

[0145] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. Examples of the photopolymerization initiator include compounds described in paragraphs

[0065] to

[0111] of JP 2014-130173 A and Japanese Patent No. 6301489 A, the contents of which are incorporated herein by reference.

[0146] Commercially available α-hydroxyketone compounds include Omnirad184, Omnirad1173, Omnirad2959, and Omnirad127 (manufactured by IGM Resins BV) (Irgacure184, Irgacure1173, Irgacure2959, and Irgacure127, respectively, manufactured by the former BASF). Commercially available α-aminoketone compounds include Omnirad907, Omnirad369, Omnirad369E, and Omnirad379EG (manufactured by IGM Resins BV) (Irgacure907, Irgacure369, Irgacure369E, and Irgacure379EG, respectively, manufactured by the former BASF). Commercially available acylphosphine compounds include Omnirad819 and OmniradTPO (both manufactured by IGM Resins BV) (Irgacure819 and IrgacureTPO, respectively, manufactured by the former BASF).

[0147] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Compounds described in JP-A-2000-066385, compounds described in JP-A-2000-080068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596 compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP 2017-198865 A, compounds described in paragraphs

[0025] to

[0038] of WO 2017 / 164127, compounds described in WO 2013 / 167515, and compounds described in WO 2019 / 088055. Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). Furthermore, it is also preferable to use, as the oxime compound, a compound that is not colorable and a compound that is highly transparent and does not easily discolor.Commercially available products include ADEKA Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0148] In the present invention, an oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A.

[0149] Alternatively, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can be used as the photopolymerization initiator. Examples of such an oxime compound include the compounds described in WO 2013 / 083505.

[0150] In the present invention, an oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0151] In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs

[0031] to

[0047] of JP 2013-114249 A, paragraphs

[0008] to

[0012] and

[0070] to

[0079] of JP 2014-137466 A, the compounds described in paragraphs

[0007] to

[0025] of Japanese Patent No. 4223071 A, and ADEKA ARCLES NCI-831 (manufactured by ADEKA Corporation).

[0152] As the photopolymerization initiator in the present invention, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0153] Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0158] As the photopolymerization initiator, a bifunctional, trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced, improving solubility in solvents and the like, making it less likely to precipitate over time, thereby improving the stability of the composition over time. Examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs

[0407] to

[0412] , and WO-A-2017 / 033680, paragraphs

[0039] to

[0055] , and compounds described in JP-A-2013-522445. Examples of the photoinitiator include the compound (E) and compound (G), Cmpd1 to Cmpd7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph

[0007] of JP-A No. 2017-523465, the photoinitiator described in paragraphs

[0020] to

[0033] of JP-A No. 2017-167399, and the photopolymerization initiator (A) described in paragraphs

[0017] to

[0026] of JP-A No. 2017-151342.

[0159] The photopolymerization initiator preferably contains an oxime compound and an α-aminoketone compound. Using both in combination improves developability and facilitates the formation of a pattern with excellent rectangularity. When using both an oxime compound and an α-aminoketone compound in combination, the amount of the α-aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass, per 100 parts by mass of the oxime compound.

[0160] The content of the polymerization initiator is preferably from 0.5 to 20% by mass, more preferably from 1.0 to 10% by mass, and even more preferably from 1.5 to 8% by mass, based on the total solid content of the composition. The composition may contain only one type of polymerization initiator, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0161] [Polymerization inhibitor] The composition may also include a polymerization inhibitor. As the polymerization inhibitor, for example, known polymerization inhibitors can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone, etc.); quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical-based polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (e.g., phenothiazine, 2-methoxyphenothiazine, etc.). Among these, phenol-based polymerization inhibitors and free radical-based polymerization inhibitors are preferred in terms of achieving better effects of the present invention.

[0162] The content of the polymerization inhibitor is preferably from 0.0001 to 0.5% by mass, more preferably from 0.001 to 0.2% by mass, and even more preferably from 0.002 to 0.05% by mass, based on the total solid content of the composition. The composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range. The ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of the polymerization inhibitor / content of the polymerizable compound (mass ratio)) is preferably 0.00005 to 0.02, more preferably 0.0001 to 0.005.

[0163] [Inorganic particles, modified inorganic particles] The compositions of the present invention may include inorganic particles or modified inorganic particles. The inorganic particles are particles different from the black pigment described above. The modified inorganic particles have inorganic particles different from the black pigment and a coating layer that covers at least a portion of the inorganic particles. In other words, the modified inorganic particles are inorganic particles having a coating layer on their surfaces.

[0164] The particle size of the inorganic particles is preferably 200 nm or less, more preferably less than 100 nm, even more preferably 10 to 90 nm, particularly preferably 20 to 80 nm, and most preferably 30 to 70 nm, in order to achieve an excellent balance between the performance and handleability of the cured film. The term "particle size" refers to the average primary particle size of particles measured by the following method. The average primary particle size can be measured using a transmission electron microscope (TEM). For example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used as the transmission electron microscope. The maximum length (Dmax: the maximum length at two points on the outline of the particle image) and the maximum perpendicular length (DV-max: the shortest distance between two lines parallel to the maximum length when the image is sandwiched between them) of a particle image obtained using a transmission electron microscope were measured, and the geometric mean value (Dmax x DV-max) was calculated. 1 / 2 The particle sizes of 100 particles were measured by this method, and the arithmetic mean value was taken as the average primary particle size of the particles.

[0165] Examples of the shape of the inorganic particles include fibrous, needle-like, plate-like, spherical, tetrapod-like, and balloon-like shapes, with spherical shapes being preferred. The inorganic particles may be in the form of monodisperse particles or aggregated particles.

[0166] The inorganic particles may be hollow particles or solid particles. Hollow particles refer to particles that have a cavity inside them. Hollow particles may have a structure consisting of an internal cavity and an outer shell surrounding the cavity. Alternatively, hollow particles may have a structure in which multiple cavities exist inside the particle. The porosity of the hollow particles is preferably 3% or more. There is no particular upper limit, but it is preferably less than 100%, more preferably 90% or less.

[0167] Examples of hollow particles include hollow silica particles described in JP-A No. 2001-233611 and Japanese Patent No. 3272111, and Surulia 4110 (trade name, manufactured by JGC Catalysts and Chemicals).

[0168] A solid particle refers to a particle that has substantially no voids inside the particle. Specifically, the porosity of the solid particles is preferably less than 3%. An example of the solid particles is IPA-ST-L (trade name, manufactured by Nissan Chemical Industries, Ltd.).

[0169] The inorganic particles may be in the form of a particle aggregate in which a plurality of inorganic particles are linked in a chain (hereinafter also referred to as beaded inorganic particles). The beaded inorganic particles are preferably formed by bonding a plurality of spherical colloidal inorganic particles having a particle diameter of 5 to 50 nm with metal oxide-containing inorganic particles. Examples of the beaded inorganic particles include silica sols described in Japanese Patent No. 4328935 and JP-A No. 2013-253145, and beaded colloidal inorganic particles are preferred.

[0170] The inorganic particles are preferably other than black. The inorganic particles may have a color such as red, blue, yellow, green, purple, orange, or white, or may be colorless. Of these, the inorganic particles are preferably white or colorless.

[0171] Examples of materials constituting the inorganic particles include inorganic oxides, inorganic nitrides, inorganic carbides, carbonates, sulfates, silicates, phosphates, and composites of two or more of these, with inorganic oxides, inorganic nitrides, and carbonates being preferred, and inorganic oxides being more preferred. Note that the inorganic particles preferably contain at least silicon.

[0172] Examples of materials that constitute inorganic particles include silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), mica compounds, zinc oxide, zirconium oxide, tin oxide, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide, and zinc sulfide. Among these, inorganic particles containing at least one selected from the group consisting of silica, titania, alumina, a mica compound, glass, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, and calcium sulfate are preferred, inorganic particles containing at least one selected from the group consisting of silica, titania, alumina, and calcium carbonate are more preferred, inorganic particles containing at least one selected from the group consisting of silica, titania, and alumina are even more preferred, and inorganic particles containing silica are particularly preferred.

[0173] The refractive index of the inorganic particles is preferably from 1.10 to 1.40, more preferably from 1.15 to 1.35.

[0174] The inorganic particles may be used alone or in combination of two or more kinds. When the inorganic particles contain silica (silicon dioxide), the content of silica (silicon dioxide) is preferably 75 to 100 mass %, more preferably 90 to 100 mass %, and even more preferably 99 to 100 mass %, based on the total mass of the inorganic particles.

[0175] The modified inorganic particles have a coating layer that coats at least a portion of the inorganic particles. In other words, the coating layer is a layer that covers part or all of the inorganic particles. That is, the coating layer may cover the entire surface of the inorganic particles or only part of the inorganic particles. The coverage rate of the inorganic particles with the coating layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, of the total surface area of ​​the inorganic particles. The upper limit is preferably 100% or less, more preferably 80% or less, of the total surface area of ​​the inorganic particles. The coating layer may be disposed directly on the surface of the inorganic particle, or may be disposed between the inorganic particle and the coating layer via another layer.

[0176] The coating layer may have a substituent, and examples of the substituent include a hydrophobic group and a substituent other than a hydrophobic group.

[0177] In the modified inorganic particles, the content of the coating layer is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total mass of the modified inorganic particles, in order to obtain better effects of the present invention. The upper limit of the content of the coating layer is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the modified inorganic particles.

[0178] The modified inorganic particles may be used alone or in combination of two or more kinds. When two or more types of modified inorganic particles are used, the total content is preferably in the following range. The total content of the inorganic particles and modified inorganic particles is preferably from 0.1 to 30.0 mass %, more preferably from 0.5 to 20.0 mass %, based on the total solid content of the composition.

[0179] [Surfactant] The composition may contain a surfactant, which contributes to improving the applicability of the composition.

[0180] Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

[0181] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781F (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 ( The above are manufactured by Sumitomo 3M Limited; Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). Block polymers can also be used as fluorine-based surfactants, and specific examples include the compounds described in JP-A-2011-089090.

[0182] When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.003 to 0.5 mass %, and even more preferably 0.005 to 0.1 mass %, based on the total solid content of the composition. The composition may contain only one surfactant, or two or more surfactants. When two or more surfactants are contained, the total amount thereof is preferably within the above range.

[0183] 〔solvent〕 The composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph

[0223] of WO 2015 / 166779, the contents of which are incorporated herein by reference. In addition, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be reduced for environmental reasons (for example, the amount may be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, based on the total amount of organic solvent).

[0184] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, organic solvents with a mass ppt (parts per trillion) level may be used, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0185] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The lower limit is preferably 1 nm or more. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0186] The organic solvent may contain isomers (compounds with the same number of atoms but different structures), and may contain only one type of isomer or multiple types of isomers.

[0187] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0188] The content of the solvent is preferably 10 to 97% by mass relative to the total amount of the composition. The lower limit is more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, even more preferably 60% by mass or more, and most preferably 65% ​​by mass or more. The upper limit is more preferably 95% by mass or less, even more preferably 80% by mass or less. The composition may contain only one solvent, or may contain two or more solvents. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0189] [Dispersion aid] The composition may also include a dispersing aid. The dispersing aid is a component other than the specific resin described above, and is a component that can suppress aggregation and / or sedimentation of components that exist in a solid state in the composition, such as the black pigment. Examples of the dispersing aid include pigment derivatives. The content of the dispersing aid is preferably from 0.01 to 10 mass %, more preferably from 0.1 to 8 mass %, and even more preferably from 0.3 to 4 mass %, based on the total solid content of the composition.

[0190] [Other optional ingredients] The composition may further contain other optional components in addition to the components described above. Examples of the additives include a coloring material other than a black pigment (which may be a pigment or a dye), an ultraviolet absorber, a silane coupling agent, a surfactant, a sensitizer, a co-sensitizer, a crosslinking agent, a curing accelerator, a heat curing accelerator, a plasticizer, a diluent, and an oil sensitizer. Furthermore, known additives such as an adhesion promoter to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) may be added as needed. These components can be found, for example, in paragraphs

[0183] to

[0228] of JP 2012-003225 A (corresponding paragraphs

[0237] to

[0309] of the specification of U.S. Patent Application Publication No. 2013 / 0034812), paragraphs

[0101] to

[0102] ,

[0103] to

[0104] , and

[0107] to

[0109] of JP 2008-250074 A, and paragraphs

[0159] to

[0184] of JP 2013-195480 A, the contents of which are incorporated herein by reference.

[0191] [Method for producing photosensitive composition] The method for producing the composition of the present invention is not particularly limited, and any known method can be used. In particular, the method for producing the composition of the present invention preferably involves producing a dispersion of the black pigment and then mixing the resulting composition with other components to form a composition. More specifically, it is preferable to produce the composition by a production method including the following steps 1 and 2. According to this method, a composition exhibiting the effects of the present invention more excellent can be obtained. Step 1: A step of mixing a pre-mixture containing a black pigment, a specific resin, and an acid compound in a bead mill to obtain a mixture (colorant dispersion, etc.) Step 2: A step of mixing the mixture with a polymerizable compound to obtain a composition (photosensitive composition)

[0192] <Process 1> The premix may contain components other than those mentioned above, and such components include, for example, a dispersing aid, a polymerization inhibitor, and a solvent. When preparing the pre-mixture to be mixed in step 1, the components contained in the pre-mixture may be mixed all at once, or may be dissolved or dispersed in a solvent and then mixed sequentially. The order of addition and working conditions for mixing are not particularly limited.

[0193] The premix is ​​mixed in a bead mill to form a mixture. When the premix contains a solvent and the mixture contains a solvent, such a mixture is also called a colorant dispersion. It is also preferable to roughly mix the pre-mixture before mixing with a bead mill. The method of rough mixing is not particularly limited, and known means can be used.

[0194] The beads used in the bead mill may be inorganic beads such as glass beads or zirconia beads, or resin beads. The bead diameter is preferably 0.01 to 1.0 mm, more preferably 0.03 to 0.65 mm. The bead filling rate is preferably 50 to 90%, more preferably 60 to 80%. The rotation speed (peripheral speed) is preferably 1 to 20 m / s, more preferably 5 to 14 m / s. The temperature of the object to be treated is preferably 5 to 80°C, more preferably 15 to 60°C. The bead mill may be, for example, any of a batch type device, a circulation type device, and a continuous type device, and a combination of a plurality of devices may be used. When the bead mill is of a batch type, the treatment time is preferably 0.5 to 6 hours, more preferably 2 to 4 hours. When the bead mill is a circulating type, the number of passes is preferably 10 to 1,000, and more preferably 60 to 200.

[0195] <Process 2> In step 2, the mixture obtained in step 1 is mixed with a polymerizable compound to obtain a composition (photosensitive composition). In step 2, at least a polymerizable compound is mixed into the mixture, and other components (polymerization initiator, polymerization inhibitor, surfactant, other resin and / or further added solvent, etc.) may also be mixed. The components (including the mixture obtained in step 1) to be mixed to obtain the composition in step 2 may be mixed all at once, or may be dissolved or dispersed in a solvent and then mixed sequentially. The order of addition and working conditions when mixing are not particularly limited. The composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet grinder, wet disperser, or the like). In the composition obtained in step 2, it is sufficient that at least a portion of the black pigment, specific resin, and acid compound contained in the composition are derived from the mixture obtained in step 1, and a black pigment, specific resin, and / or acid compound, etc., other than the components contained in the mixture may be further mixed in step 2.

[0196] The composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without particular limitation. Examples of such filters include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these, polypropylene (including high density polypropylene) or nylon is preferred. The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, even more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. This range makes it possible to reliably remove fine foreign matter, such as impurities and aggregates contained in the pigment, while suppressing clogging of the pigment (including black pigment). The composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, alkalis, etc. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably substantially free of impurities (below the detection limit of the measuring device). The above impurities can be measured using an inductively coupled plasma mass spectrometer (Agilent 7500cs model, manufactured by Yokogawa Analytical Systems).

[0197] [Method of manufacturing the cured film] In this specification, the term "cured film" refers to a film formed by subjecting a composition layer formed using the composition of the present invention to a curing treatment such as exposure treatment. The method for producing the cured film is not particularly limited, but preferably includes the following steps: By going through the following steps, for example, a patterned cured film can be formed. Each step will be described below.

[0198] [Composition layer forming step] In the composition layer forming step, prior to exposure, a composition layer (composition layer) is formed by applying the composition onto a support or the like. The support may be, for example, a substrate for a solid-state imaging device, in which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (e.g., a silicon substrate). If necessary, a primer layer may be provided on the support to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface.

[0199] Examples of methods for applying the composition to a support include various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing. The film thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. The composition layer coated on the support can be dried (prebaked) at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate or oven.

[0200] [Exposure process] The exposure step is a step of irradiating the composition layer formed in the composition layer-forming step with actinic rays or radiation to expose it. Specifically, the exposure step is a step of irradiating the composition layer formed in the composition layer-forming step with actinic rays or radiation to expose it, thereby curing the light-irradiated region of the composition layer. The method of light irradiation is not particularly limited, but it is preferable to irradiate with light through a photomask having patterned openings. The exposure is preferably carried out by irradiation with radiation, and the radiation that can be used for exposure is preferably ultraviolet light such as g-ray, h-ray, and i-ray, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is 5 to 1500 mJ / cm. 2 is preferred, and 10 to 1000 mJ / cm 2 is more preferred. When the composition contains a thermal polymerization initiator, it is also preferable to heat the composition layer in the exposure step. The heating temperature is not particularly limited, but is preferably 80 to 250° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds. In addition, when the composition layer is heated in the exposure step, this may also serve as a post-heating step described later. In other words, when the composition layer is heated in the exposure step, the method for producing a cured film does not need to include a post-heating step.

[0201] [Development process] The development step is a step of carrying out a development treatment on the composition layer after exposure. This step dissolves the composition layer in the unexposed region in the exposure step, leaving only the photocured portion. For example, when the exposure step is carried out by irradiating light through a photomask having a patterned opening, a patterned cured film is obtained. The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage the underlying image pickup element and circuits is preferred. The development temperature is, for example, 20 to 30°C. The developing time is, for example, 20 to 90 seconds. In recent years, the developing time may be extended to 120 to 180 seconds to further remove residues. Furthermore, to further improve residue removal, the developer may be shaken off every 60 seconds and new developer may be supplied, and this process may be repeated several times.

[0202] The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass). Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred). When an alkaline developer is used, a washing treatment with water is generally carried out after development.

[0203] [Post-bake] After the exposure step, it is preferable to carry out a heat treatment (post-baking). Post-baking is a heat treatment after development to complete curing. The heating temperature is preferably 240°C or less, more preferably 220°C or less. There is no particular lower limit, but in consideration of efficient and effective processing, it is preferably 50°C or more, more preferably 100°C or more. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0204] The post-baking is preferably carried out in an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but a concentration of 10 ppm by volume or more is preferred.

[0205] Further, instead of the post-baking by heating, the curing may be completed by UV (ultraviolet) irradiation. In this case, the composition preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for a typical i-line exposure lithography process. Examples of UV curing agents include Chiba Ilgacure 2959 (trade name). When UV irradiation is performed, the composition layer is preferably a material that cures at a wavelength of 340 nm or less. While there is no particular lower limit for the wavelength, it is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5,000 mJ, more preferably 300 to 4,000 mJ, and even more preferably 800 to 3,500 mJ. This UV curing process is preferably performed after the lithography process to more effectively perform low-temperature curing. An ozone-free mercury lamp is preferably used as the exposure light source.

[0206] [Physical properties and uses of cured films] [Physical properties of cured film] The cured film formed using the composition of the present invention (particularly the composition of the present invention containing a black coloring material) has an optical density (OD) per 1.5 μm film thickness in the wavelength range of 400 to 1100 nm of preferably 2.5 or more, more preferably 3.0 or more, in order to have excellent light-shielding properties. The upper limit is not particularly limited, but is generally preferably 10 or less. The above cured film can be preferably used as a light-shielding film. In this specification, an optical density of 2.5 or more per 1.5 μm film thickness in the wavelength region of 400 to 1100 nm means that the optical density per 1.5 μm film thickness is 2.5 or more over the entire wavelength region of 400 to 1100 nm. In this specification, the method for measuring the optical density of a cured film involves first forming a cured film on a glass substrate, measuring it using an integrating sphere type light-receiving unit of a spectrophotometer U-4100 (product name, manufactured by Hitachi High-Technologies Corporation), measuring the film thickness at the measurement point, and calculating the optical density per predetermined film thickness. The thickness of the cured film is, for example, preferably 0.1 to 4.0 μm, more preferably 1.0 to 2.5 μm, and may be thinner or thicker than this range depending on the application. When the cured film is used as a light-damping film, the light-shielding properties may be adjusted by making the film thinner than the above range (for example, 0.1 to 0.5 μm). In this case, the optical density per 1.0 μm of film thickness in the wavelength range of 400 to 1200 nm is preferably 0.1 to 1.5, more preferably 0.2 to 1.0.

[0207] The reflectance of the cured film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is preferably 0% or more. The reflectance is determined from the reflectance spectrum obtained by irradiating light with a wavelength of 400 to 1100 nm at an incident angle of 5° using a VAR unit of a V7200 (trade name) spectrometer manufactured by JASCO Corporation. Specifically, the reflectance of light with the wavelength showing the maximum reflectance in the wavelength range of 400 to 1100 nm is defined as the reflectance of the cured film.

[0208] The cured film is also suitable for light-shielding members and light-shielding films, as well as anti-reflection members and anti-reflection films, of optical filters and modules used in portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer / multifunction devices and scanners; industrial devices such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras, and devices with identity authentication functions using facial image recognition or biometric authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; and space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy and deep space target exploration cameras.

[0209] The cured film can also be used in applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).The cured film is suitable for optical filters and optical films used in micro LEDs and micro OLEDs, as well as for components that provide a light-blocking function or an anti-reflection function. Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

[0210] The cured film is also suitable as an optical film for use in quantum dot sensors and quantum dot solid-state imaging devices. It is also suitable as a component imparting light-shielding and anti-reflection functions. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in U.S. Patent Application Publication No. 2012 / 37789 and WO 2008 / 131313.

[0211] [Light-shielding film, optical element, solid-state imaging element, and solid-state imaging device] The cured film of the present invention is also preferably used as a so-called light-shielding film, and such a light-shielding film is also preferably used in a solid-state imaging device. As described above, a cured film formed using the light-shielding composition of the present invention has excellent light-shielding properties and low reflectivity. The light-shielding film is one of the preferred applications of the cured film of the present invention, and the light-shielding film of the present invention can be produced in the same manner as the method for producing the cured film described above. Specifically, the light-shielding film can be produced by applying a composition to a substrate to form a composition layer, exposing the composition to light, and developing the composition layer.

[0212] The present invention also includes an invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned cured film (light-shielding film). Examples of the optical element include optical elements used in optical instruments such as cameras, binoculars, microscopes, and semiconductor exposure devices. Among these, the optical element is preferably a solid-state image pickup element mounted in a camera or the like.

[0213] The solid-state imaging device of the present invention is a solid-state imaging device that includes the above-mentioned cured film (light-shielding film) of the present invention. Examples of the solid-state imaging element of the present invention that includes a cured film (light-shielding film) include an embodiment in which a substrate has a plurality of photodiodes and light-receiving elements made of polysilicon or the like that constitute the light-receiving area of ​​the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.), and the support has a cured film on the light-receiving element forming surface side (for example, parts other than the light-receiving section and / or color-adjusting pixels, etc.) or on the opposite side of the forming surface. Furthermore, when the cured film is used as a light attenuating film, the dynamic range of the solid-state imaging device can be improved by arranging the light attenuating film so that part of the light passes through the light attenuating film and then enters the light receiving element. A solid-state imaging device includes the above-described solid-state imaging element.

[0214] [Image display device] The cured film obtained using the composition of the present invention is also preferably applied to image display devices. The image display device of the present invention includes a cured film obtained using the composition of the present invention. An example of an image display device having a cured film is one in which the cured film is included in a black matrix, and a color filter including such a black matrix is ​​used in the image display device. Next, a black matrix and a color filter including a black matrix will be described, and further, as a specific example of an image display device, a liquid crystal display device including such a color filter will be described.

[0215] <Black matrix> The cured film obtained using the composition of the present invention is also preferably contained in a black matrix, which may be contained in a color filter, a solid-state imaging device, or an image display device such as a liquid crystal display device.

[0216] <Color filter> The cured film obtained using the composition of the present invention is also preferably contained in a color filter. The form of the color filter including the cured film is not particularly limited, but may be a color filter including a substrate and the black matrix, i.e., a color filter including red, green, and blue colored pixels formed in openings of the black matrix formed on the substrate.

[0217] <Liquid crystal display device> The cured film obtained using the composition of the present invention is also preferably included in a liquid crystal display device. The liquid crystal display device may include a cured film in any form, but examples thereof include a form including a color filter including the black matrix (cured film) as described above.

[0218] The liquid crystal display device may have, for example, a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates. The substrates are as already described as the substrates for the black matrix.

[0219] A specific example of the liquid crystal display device is a laminate including, from the user's side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) element / substrate / polarizing plate / backlight unit in this order.

[0220] [Infrared sensor] The cured film obtained using the composition of the present invention is also preferably included in an infrared sensor. Next, a solid-state imaging device to which the above-described infrared sensor is applied will be described. The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, etc. Note that for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, the contents of which are incorporated herein by reference.

[0221] [Headlight unit] The cured film of the present invention is also preferably included as a light-shielding film in a headlight unit of a vehicle lamp such as an automobile. More specifically, the headlight unit of the present invention has a light source and a light-shielding part that blocks at least a portion of the light emitted from the light source, and the cured film of the present invention is applied to the light-shielding part. The cured film of the present invention included in the headlight unit is preferably formed in a pattern so as to block at least a portion of the light emitted from the light source. [Example]

[0222] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0223] [Production of colorant dispersion liquid] 100 g of titanium oxide MT-150A (trade name: manufactured by Teika Co., Ltd.) with an average particle size of 15 nm and a BET surface area of ​​300 m 225 g of AEROGIL® 300 / 30 silica particles (manufactured by Evonik) with a molecular weight of 1 / g and 100 g of dispersant Disperbyk 190 (trade name: manufactured by BYK-Chemie) were weighed out, and 71 g of electro-ionized water was added. A uniform aqueous mixture was obtained by processing for 20 minutes using a KURABO MAZERSTAR KK-400W at an orbital speed of 1360 rpm and a rotation speed of 1047 rpm. This aqueous solution was filled into a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama). The atmosphere was then replaced with nitrogen, and ammonia gas was flowed at 100 mL / min at the same temperature for 5 hours to carry out a nitriding / reduction treatment. After completion, the recovered powder was pulverized in a mortar to obtain a powder containing Si atoms with a specific surface area of ​​73 m. 2 / g of titanium black (a-1) [dispersed material containing titanium black particles and Si atoms] was obtained. To the titanium black (a-1) (25.00 parts by mass) prepared above, specific resin X-1 (7.37 parts by mass) and evaluation compound S-1 (0.13 parts by mass) were added, and propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone were added in a ratio (mass ratio) of 74.6 to 25.4 so that the total amount of the liquid was 100 parts by mass, thereby obtaining a dispersion. The obtained dispersion was thoroughly stirred with a stirrer to perform premixing. The obtained dispersion was subjected to a dispersion treatment under the following conditions using an NPM Pilot (bead mill) manufactured by Shinmaru Enterprises, to obtain colorant dispersion AA1.

[0224] (dispersion condition) Bead diameter: φ0.05mm Bead filling rate: 65% by volume Mill peripheral speed: 10m / sec Separator peripheral speed: 11m / s Amount of mixed liquid to be dispersed: 15.0 kg ·Circulation flow rate (pump supply amount): 60kg / hour Treatment liquid temperature: 20~25℃ Cooling water: Tap water at 5°C Bead mill annular passage internal volume: 2.2L Number of passes: 84

[0225] The specific resin X-1 and the compound S-1 to be evaluated used in the production of the colorant dispersion AA1 are as follows. In the colorant dispersions described below, X-1 and S-1 are the same compounds.

[0226] S-1: Compound with the structure shown below

[0227] [ka]

[0228] Specific resin X-1: a resin having the structure shown below (weight average molecular weight 18,000, acid value 67.0 mgKOH / g, carbon-carbon double bond equivalent 0.70 mmol / g, the numbers attached to each repeating unit indicate the molar ratio of each repeating unit)

[0229] [ka]

[0230] Colorant dispersions AA2 to AA52 and AB1 to AB5 were produced in the same manner as colorant dispersion AA1, except that the type or amount of the evaluation compound, or the type or amount of the specific resin, was changed as shown in Tables 1 to 10. Unless otherwise specified, the numerical values ​​in the table represent parts by mass. TiBk represents Titanium Black (a-1), and "D90 (nm)" represents the 90% diameter of Titanium Black in the colorant dispersion. For AA47, two types of evaluation compounds were blended, and "S-1 / S-2 1:1" in the table means that the blending amounts (mass ratio) of S-1 and S-2 were 1:1. Similarly, for AA48 to AA52, the results are for blending two types of evaluation compounds.

[0231] [Table 1]

[0232] [Table 2]

[0233] [Table 3]

[0234] [Table 4]

[0235] [Table 5]

[0236] [Table 6]

[0237] [Table 7]

[0238] [Table 8]

[0239] [Table 9]

[0240] [Table 10]

[0241] [Resins and compounds evaluated] The specific structures of Resin X-2 and the evaluation compounds in the above table are shown below. The compounds to be evaluated were acid compounds S-1 to S-39 or comparative compound S-40.

[0242] Resin X-2 (a resin other than the specified resin, comparable to X-1): a resin with the following structure (weight average molecular weight 20,000, acid value 74.9 mg KOH / g, the numbers attached to each repeating unit indicate the molar ratio of each repeating unit)

[0243] [ka]

[0244] Evaluated compounds

[0245] [ka]

[0246] [ka]

[0247] Tables 11 to 15 show the molecular weights and pKa of the compounds evaluated. In the table, the column "Mw" indicates the molecular weight of the compound being evaluated. In the table, the "pKa" column indicates the pKa of the evaluation compound. The multiple values ​​listed in the "pKa" column represent the pKa derived from the carboxy group contained in each evaluation compound. For example, evaluation compound S-1 has two carboxy groups with a pKa of 4.06.

[0248] [Table 11]

[0249] [Table 12]

[0250] [Table 13]

[0251] [Table 14]

[0252] [Table 15]

[0253] [Production of composition (photosensitive composition)] The raw materials shown below were mixed in the amounts (parts by mass) shown in Tables 16 to 23 to obtain compositions (photosensitive compositions) of Examples and Comparative Examples.

[0254] 〔solvent〕 PGMEA: Propylene glycol monomethyl ether acetate

[0255] [Resin (post-added resin)] The resin (post-added resin) is the specific resin or other resins. B-1: Resin having the structure shown below (weight average molecular weight 11,000, acid value 32.0 mgKOH / g, the numbers attached to each repeating unit indicate the molar ratio of each repeating unit)

[0256] [ka]

[0257] B-2: Cardo resin V-259ME (Nippon Steel Sumitomo Metal Corporation) B-3: Resin with the structure shown below (weight average molecular weight 18300, acid value 66.7 mgKOH / g) Here, r, s, t, and u respectively represent the molar ratios of the respective repeating units, and r / s / t / u=2.6 / 65.1 / 12.3 / 20 (mol %).

[0258] [ka]

[0259] B-4: Resin having the structure shown below (weight average molecular weight 12,000, acid value 33.1 mgKOH / g, the numbers attached to each repeating unit indicate the molar ratio of each repeating unit)

[0260] [ka]

[0261] [Polymerizable compound] M-1: KAYARAD DPHA (Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) M-2: Aronix TO-2349 (acid-modified multifunctional acrylate, manufactured by Toagosei Co., Ltd.) M-3: KAYARAD RP-1040 (Nippon Kayaku Co., Ltd.) M-4: M-305 (pentaerythritol tetraacrylate, manufactured by Toagosei Co., Ltd.)

[0262] [Polymerization initiator] Ini-1: IRGACURE OXE02 (BASF) Ini-2: Oxime ester polymerization initiator (structural formula below)

[0263] [ka]

[0264] Ini-3: Oxime ester polymerization initiator (structural formula below)

[0265] [ka]

[0266] Ini-4: NCI-831 (ADEKA) Ini-5: N-1919 (ADEKA) Ini-6: NCI-930 (ADEKA) Ini-7: Initiator with the following structural formula

[0267] [ka]

[0268] [Polymerization inhibitor] A-1: p-Methoxyphenol A-2: The following compound (wherein t-Bu represents a tert-butyl group):

[0269] [ka]

[0270] [Surfactant] W-1: The following surfactant (weight average molecular weight 15,000, the numbers or letters attached to each repeating unit indicate the molar ratio of each repeating unit):

[0271] [ka]

[0272] W-2: The following surfactant (weight average molecular weight: 3000, where n represents an integer of 1 or more):

[0273] [ka]

[0274] W-3: KF6000 (Shin-Etsu Silicone Co., Ltd.) W-4: FZ-2122 (Toray Dow Chemical Co., Ltd.)

[0275] 〔silica〕 T-1: PMA-ST-L (surface-modified solid silica, manufactured by Nissan Chemical Industries, Ltd.)

[0276] [Coloring material dispersion] Each of the colorant dispersions AA1 to AA52 or AB1 to AB5 prepared as described above

[0277] [evaluation] [Preparation of a patterned light-shielding film substrate using a composition] The composition obtained above was applied to a glass substrate by spin coating to form a coating film with a dry thickness of 1.5 μm. The resulting coating film was prebaked at 80°C for 90 seconds, and then exposed to a high-pressure mercury lamp (lamp power 50 mW / cm) using a UX-1000SM-EH04 (manufactured by Ushio Inc.) through a mask with an L / S pattern (line width:space width = 1:1) with an opening line width of 50 μm. 2 ) at 500mJ / cm 2 The coating film was exposed to light by proximity exposure at an exposure dose of 1000 kJ / cm. Next, the exposed coating film was puddle-developed with a developer "CD-2060" (manufactured by Fujifilm Electronic Materials Co., Ltd.) using AD-1200 (manufactured by Mikasa Co., Ltd.) for 15 seconds, and then washed with pure water using a shower nozzle for 30 seconds to remove uncured portions of the coating film. The coating film was then post-baked at 220°C for 300 seconds to obtain a patterned light-shielding film substrate.

[0278] [Residue Evaluation] For the patterned light-shielding film substrates prepared using each composition by the above-mentioned method, the space areas (non-exposed areas) on the substrate where no pattern was formed were observed using a transmission microscope and evaluated based on the following evaluation criteria. If the evaluation was A or B, it was determined that there was no problem in practical use. (Evaluation criteria) A: No residue is present in the space. B: Residue is observed in less than 33.3% of the space area. C: Residue is observed in 33.3% or more of the space area.

[0279] [Evaluation of adhesion (peeling)] Patterned light-shielding film substrates were prepared using each composition in the same manner as described above, except that the opening line width of the mask used during exposure was changed to 10 μm and the exposure dose was changed. The resulting patterned light-shielding film substrate was observed with an optical microscope to check for 10 μm-wide line patterns, and evaluated for the presence or absence of pattern peeling based on the following evaluation criteria. A rating of A or B was deemed to be satisfactory for practical use. The smaller the exposure dose that allows formation of a pattern (image area) that adheres to the substrate and does not peel off, the more preferable. (Evaluation criteria) A: A pattern without peeling can be formed with an exposure dose of 1000 mJ or less. B: A pattern without peeling can be formed with an exposure dose of more than 1000 mJ and not more than 1400 mJ. C: A pattern without peeling can be formed with an exposure dose of more than 1400 mJ.

[0280] [Undercut width evaluation (UC evaluation)] A patterned light-shielding film substrate was prepared using each composition in the same manner as above, except that the opening line width of the mask used during exposure was changed to 300 μm. The resulting patterned light-shielding film substrate was observed using a scanning electron microscope S-4800 (Hitachi High-Technologies Corporation) to obtain a cross-sectional SEM image of the 300 μm-wide pattern, and the undercut width was measured and evaluated based on the following evaluation criteria. A rating of A or B was deemed to be satisfactory for practical use. The undercut width is defined as "(the line width at the widest point in the cross section of the pattern) - (the line width at the point where the line pattern contacts the substrate in the cross section of the pattern) ÷ 2." The "line width at the widest point in the cross section of the pattern" is 300 μm. (Evaluation criteria) A: Undercut width less than 1.2 μm B: Undercut width is 1.2 μm or more and less than 1.8 μm C: Undercut width is 1.8 μm or more

[0281] [Evaluation of storage stability] For each composition obtained above, the viscosity (mPa s) of the composition before standing was measured using an RE-85L (manufactured by Toki Sangyo Co., Ltd.) under the measurement conditions shown below. After the above measurements, the composition was left standing at 7°C in the dark for 360 days (standing treatment), and then the viscosity (mPa s) of the composition after standing treatment was measured using an RE-85L (manufactured by Toki Sangyo Co., Ltd.) under the measurement conditions shown below. 《Viscosity measurement conditions》 The viscosity of the composition before and after the above-mentioned standing treatment was measured in a laboratory controlled at a temperature of 22±5°C and a humidity of 60±20%, with the temperature of the composition adjusted to 23°C.

[0282] The viscosity stability over time was evaluated based on the rate of change in viscosity before and after the standing treatment, according to the following criteria. A rating of A or B was deemed acceptable for practical use. The rate of change in viscosity was calculated using the following formula. Viscosity change rate (%) = ((viscosity of composition after storage / viscosity of composition before storage) - 1) × 100 (Evaluation criteria) A: The absolute value of the viscosity change rate is within 10%. B: The absolute value of the viscosity change rate is more than 10% and less than 15%. C: The absolute value of the viscosity change rate is more than 15%.

[0283] [result] The following table shows the composition formulation, characteristics of the compounds used for evaluation, and the evaluation results. The composition formulations in the table indicate the blending amounts (parts by mass) of each component. In the table, the "Amount (%)" column in the "Evaluation Compound" column indicates the content of the evaluation compound relative to the total solid content in the composition of each Example or Comparative Example. In Example 164, two types of evaluation compounds were blended, and "S-1 / S-2 1:1" in the table means that the blending amounts (mass ratio) of S-1 and S-2 was 1:1. Similarly, in Examples 165 to 169, the results are for blending two types of evaluation compounds.

[0284] [Table 16]

[0285] [Table 17]

[0286] [Table 18]

[0287] [Table 19]

[0288] [Table 20]

[0289] [Table 21]

[0290] [Table 22]

[0291] [Table 23]

[0292] The "B-1(*)" in the column for the evaluation compound in Comparative Example 105 indicates that, unlike the other Examples, the evaluation compound used was the above-mentioned B-1, which does not fall under the category of the acid compounds described above. The above B-1 does not fall under the category of the acid compounds in terms of molecular weight. The optical density of the cured film (light-shielding film) obtained using the composition of each example by changing the patterned exposure described in the above [Preparation of patterned light-shielding film substrate using composition] to full-surface exposure was 2.5 or more per 1.5 μm film thickness in the wavelength range of 400 to 1100 nm.

[0293] From the results in Tables 16 to 23, it was confirmed that the composition of the present invention can form a pattern with excellent adhesion, can suppress residue, and also has excellent storage stability.

[0294] A comparison of Examples 102 and 103 with Example 101 revealed that when the content of the acid compound was 0.8 mass% or more relative to the total solid content of the composition, the residue suppression and storage stability were better, and a comparison of Examples 101 and 102 with Example 103 revealed that when the content of the acid compound was 2.0 mass% or less, the adhesion and UC evaluation were better.

[0295] Comparison between Example 106 and Example 107 and the like revealed that when the acid compound was an aliphatic carboxylic acid, the residue suppression property was more excellent.

[0296] Comparison of Example 111 with Examples 109 and 112 and the like revealed that when the pKa of the acid compound was 3.00 to 5.00, the adhesion and UC evaluation were more excellent.

[0297] Comparison of Example 122 and Example 127 with Example 135 and the like revealed that when the acid compound had two or three carboxy groups, the adhesion and UC evaluation were more excellent.

[0298] Comparison of Examples 160 to 163 and the like reveals that better effects can be obtained when the mass ratio of the content of the acid compound to the content of the specific resin is 2 / 98 to 15 / 85.

[0299] Comparison of Examples 164 to 169 with Example 101 revealed that better effects were obtained when two types of acid compounds were used.

Claims

1. A black pigment; a resin having a graft chain and a carbon-carbon double bond; an acid compound having two or more carboxy groups and a molecular weight of 50.0 to 550.0; A photosensitive composition comprising a polymerizable compound, the content of the acid compound is 0.3 to 5.0 mass % based on the total solid content of the photosensitive composition, the black pigment is a nitride or oxynitride of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron, the resin functions as a dispersant for the black pigment; The photosensitive composition for alkaline development, wherein the acidic compound is a compound represented by formula (A): 【Chemistry 1】 L a represents an n-valent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent selected from the group consisting of a hydroxy group, a halogen atom, and an alkyloxycarbonyl group, or an n-valent aromatic ring group which may have a substituent selected from the group consisting of a hydroxy group, a halogen atom, and an alkyloxycarbonyl group, and n represents an integer of 2 or more.

2. 2. The photosensitive composition of claim 1, wherein the acid compound is an aliphatic carboxylic acid.

3. 3. The photosensitive composition according to claim 1, wherein the acid compound has two or three carboxy groups.

4. 4. The photosensitive composition according to claim 1, wherein the acid compound has a pKa of 0.00 to 6.

00.

5. 5. The photosensitive composition according to claim 1, wherein the acid compound has 1 to 34 carbon atoms.

6. 6. The photosensitive composition according to claim 1, wherein the content of the acid compound is 0.8 to 2.0% by mass based on the total solid content of the photosensitive composition.

7. 7. The photosensitive composition according to claim 1, wherein a mass ratio of the content of the acid compound to the content of the resin is 2 / 98 to 15 / 85.

8. 8. The photosensitive composition according to claim 1, wherein the graft chains have a polyester structure.

9. 9. The photosensitive composition according to claim 1, comprising two or more of the acid compounds.

10. The photosensitive composition according to any one of claims 1 to 9, further comprising a photopolymerization initiator.

11. A method for producing the photosensitive composition according to any one of claims 1 to 10, comprising the steps of: Step 1: Mixing a pre-mixture containing the black pigment, the resin, and the acid compound in a bead mill to obtain a mixture; and a step 2 of mixing the mixture with the polymerizable compound to obtain the photosensitive composition.

12. A cured film formed using the photosensitive composition according to any one of claims 1 to 10.

13. A color filter comprising the cured film according to claim 12.

14. A light-shielding film comprising the cured film according to claim 12.

15. An optical element comprising the cured film according to claim 12.

16. A solid-state imaging device comprising the cured film according to claim 12.

17. A headlight unit for a vehicle lamp, A light source and a light-shielding portion that blocks at least a portion of the light emitted from the light source, A headlight unit, wherein the light-shielding portion comprises the cured film according to claim 12.

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