Photosensitive composition, cured product, black matrix, black bank, color filter, image display panel, image display device, method for producing cured product, and compound

Abstract

To provide a photosensitive composition that is excellent in sensitivity and developability and can form a cured product with superior light-blocking properties.SOLUTION: A photosensitive composition comprises an alkali-soluble polymer (A), a polymerizable compound (B), a photopolymerization initiator (C), and a compound (D) represented by the formula (1) in the figure. [In the formula, R1 and R2 each represent a hydrogen atom or a leaving group, where one of R1 and R2 is a leaving group; R3 and R4 independently represent a bromine atom, chlorine atom, fluorine atom, organic group, nitro group, carboxyl group, or sulfo group.]SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition, a cured product, a black matrix, a black bank, a color filter, an image display panel, an image display device, a method for producing a cured product, and a compound. [Background technology]

[0002] In a display device, a patterned light-shielding member such as a black matrix, a black bank, etc. is usually formed. As a material used for forming such a light-shielding member, various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator have been proposed.

[0003] For example, negative photosensitive compositions containing black agents such as benzofuranone-based black pigments, perylene-based black pigments, and azo-based black pigments, which are highly sensitive and capable of forming patterns of desired shapes, are known (e.g., Patent Document 1), and photosensitive resin compositions containing lactam-based pigments, which can achieve both pattern formability and suppression of the generation of residues after development, are known (e.g., Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 181311 [Patent Document 2] Patent Publication No. 2021-64467 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the black pigments that have been used in conventional photosensitive compositions such as those described in Patent Documents 1 and 2 usually have low solubility and dispersibility in the solvent contained in the photosensitive composition, and are generally used in combination with a dispersant. In addition, they have problems such as insufficient developability, which can lead to residues (foreign matter) being generated in areas removed by development after development.

[0006] On the other hand, in response to the demand for higher quality display elements accompanying the recent expansion of the uses of display devices, there has been a demand for photosensitive compositions that are excellent in sensitivity and developability and can form cured products with excellent light-shielding properties in order to improve the quality (e.g., higher definition and higher light-shielding properties) of light-shielding members such as black matrices and black banks of display elements. However, increasing the light-shielding properties leads to poor transmittance to radiation (especially g-rays, h-rays, and i-rays) during exposure, resulting in a trade-off between the two.

[0007] The present invention has been made in consideration of the above, and an object of the present invention is to provide a photosensitive composition that is excellent in sensitivity and developability, and is also capable of forming a cured product that has excellent light-shielding properties. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by the following configuration examples. That is, according to the present invention, the following photosensitive composition, cured product, black matrix, black bank, color filter, image display panel, image display device, method for producing the cured product, and compound are provided. A configuration example of the present disclosure is shown below. [1] A photosensitive composition comprising an alkali-soluble polymer (A), a polymerizable compound (B), a photopolymerization initiator (C), and a compound (D) represented by the following formula (1): [ka] [In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a leaving group; R 1 and R 2 at least one of is a leaving group, R 3 and R 4 each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2are each independently an integer of 0 to 4. [2] The photosensitive composition according to [1] above, wherein the leaving group is a methoxymethyl group or a tert-butoxycarbonyl group. [3] The photosensitive composition according to [1] or [2] above, further comprising a black pigment or carbon black. [4] A cured product obtained by curing the photosensitive composition according to any one of [1] to [3] above. [5] A black matrix or black bank comprising the cured product according to [4] above. [6] A color filter comprising the black matrix described in [5] above. [7] An image display panel comprising the color filter according to [6]. [8] An image display device comprising the image display panel according to [7]. [9] An image display device comprising the black bank described in [5].

[10] A step of applying the photosensitive composition according to any one of the above [1] to [3] onto a substrate to form a coating film; site-selectively exposing the coating to light; developing the exposed coating; and heating the developed pattern.

[11] The method according to

[10] above, wherein the patterned cured product is a black matrix or a black bank.

[12] A compound represented by the following formula (3): [ka] [In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally labile group which is eliminated at a heating temperature of 250° C. or less, and R 5 and R 6 at least one of the groups is the thermally detachable group, R 3 and R 4each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2 are each independently an integer of 0 to 4. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive composition which is excellent in sensitivity and developability (particularly alkali solubility) and is capable of forming a cured product having excellent light-shielding properties. By using the photosensitive composition according to one embodiment of the present invention, it is possible to form a cured product that is highly reliable, leaves little residue (foreign matter) in areas to be removed by development, has excellent adhesion to the substrate, and has excellent light-blocking properties in a desired shape (e.g., can be made highly precise). Furthermore, the photosensitive composition according to one embodiment of the present invention exhibits the above-mentioned effects even when no dispersant is used. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 shows the pattern obtained from the photosensitive composition obtained in Example 1 and the UV-visible absorbance spectrum of the pattern after heating at 230° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "to" means that the numerical range includes the numerical ranges before and after "to" as the lower and upper limits.

[0012] In this specification, the term "(meth)acrylic" encompasses both "acrylic" and "methacrylic." The term "(meth)acryloyl group" encompasses both "acryloyl group" and "methacryloyl group."

[0013] "Alkali-soluble" means that it is soluble in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 25°C. Incidentally, a polymer can be said to be alkali-soluble when 1 g or more of the polymer dissolves in 100 g of a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 25° C. Whether or not the polymer dissolves can be determined by the presence or absence of a precipitate.

[0014] ≪Photosensitive composition≫ The photosensitive composition of the present disclosure (hereinafter also referred to as "the composition") contains an alkali-soluble polymer (A) (hereinafter also referred to as "component (A)"), a polymerizable compound (B) (hereinafter also referred to as "component (B)"), a photopolymerization initiator (C) (hereinafter also referred to as "component (C)"), and a compound (D) represented by formula (1) (hereinafter also referred to as "component (D)"). Unless otherwise specified, each component may be used alone or in combination of two or more kinds.

[0015] The present composition is a composition that is excellent in sensitivity and developability (particularly alkali solubility), and is also capable of forming a cured product that has excellent light-shielding properties. Conventionally, in forming a black light-shielding pattern, a black resist in which carbon black, a perylene pigment, a lactam pigment, or the like is dispersed in a solvent using a dispersant is exposed, developed, baked, etc. However, there is a problem that increasing the light-shielding property reduces the sensitivity and resolution of the resist because radiation, etc. cannot pass through during exposure. As mentioned above, conventionally, pigments are dispersed in a solvent using a dispersant, but it is difficult to disperse the pigments uniformly, and there is a problem that poorly dispersed areas remain as residues during development. In one embodiment of the present invention, it is preferable to introduce a thermally soluble group having excellent solvent solubility into the lactam pigment, which can solve these problems. This allows the lactam pigment to be dissolved in the solvent at the molecular level, and the generation of residues during development can be significantly suppressed.

[0016] In addition, by introducing a (thermal) detachable group, the transmittance of radiation can be increased as shown in FIG. 1, and the sensitivity can be increased. Furthermore, by baking (post-baking) at a temperature at which the thermally detachable group is detached, the thermally detachable group contained in component (D) is decomposed and gasified, and component (D) can return from the dye to the original lactam pigment. Therefore, the baking can exhibit the light-shielding properties that lactam pigments inherently possess. In addition, there is an advantage that the "dye migration" described later, which is a problem for dyes when the thermally detachable group is decomposed and loses solubility in a solvent, is unlikely to occur. Furthermore, this composition does not use a dispersant, or even if a dispersant is used, a smaller amount than conventional ones is sufficient, so there is also an advantage that the generation of fumes and decomposition products derived from the dispersant during baking can be suppressed.

[0017] Furthermore, since the component (D) has excellent solubility in solvents, the present composition can provide a desired (uniform) photosensitive composition even without using a dispersant, thereby achieving the above-mentioned effects. When a cured product such as a black matrix or a black bank is formed from the present composition, suppression of outgassing and the like may be required depending on the application of the cured product, such as an image display device, but by using the component (D), which has excellent solubility in solvents, a desired (uniform) photosensitive composition can be obtained without using a dispersing agent, and by not using a dispersing agent, problems such as outgassing derived from the dispersing agent can be suppressed.

[0018] Furthermore, the component (D) can be called a so-called "dye" that has excellent solubility in a solvent, but when the component (D) is post-baked to eliminate the leaving group as described above, the solubility of the component (D) in a solvent decreases, and the component (D) becomes a so-called "pigment." Therefore, for example, when post-baking is performed to form a cured product, the cured product contains the "pigment" derived from the component (D). If the cured product contains a so-called "dye," the dye may bleed out of the cured product (e.g., black matrix, black bank) and migrate to other components of the device, such as an image display device, in which the cured product is used, such as a light-emitting layer, resulting in so-called "dye migration," which may cause black spots and the like on the other components. On the other hand, by post-baking component (D) as described above, the component contained in the obtained cured product can be made a "pigment" rather than a "dye," and the dye migration can be suppressed.

[0019] [Component (A): alkali-soluble polymer (A)] The component (A) is not particularly limited as long as it is an alkali-soluble polymer, but for example, a polymer having an acidic group such as a carboxy group, an acid anhydride group, a phenolic hydroxyl group, or a fluorinated hydroxyalkyl group (a hydroxyalkyl group in which some of the hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms) is preferred.

[0020] Examples of the polymer having an acidic group include polymers having a phenolic hydroxyl group, such as novolac resin, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, polybenzoxazole precursor, polyhydroxystyrene, and copolymers obtained using hydroxystyrene and styrene; and polymers having a carboxy group, such as carboxy group-containing epoxy (meth)acrylate resins having a novolac type skeleton in the main chain, and polyamic acids.

[0021] In addition, examples of the polymer having an acidic group include a copolymer of an ethylenically unsaturated monomer having one or more acidic groups (hereinafter also referred to as "unsaturated monomer (a1)") and another ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (a1) (hereinafter also referred to as "unsaturated monomer (a2)"). In particular, a (meth)acrylic polymer having an acidic group is preferred. The unsaturated monomers (a1) and (a2) can each be used alone or in combination of two or more.

[0022] Examples of the unsaturated monomer (a1) include carboxy group-containing unsaturated monomers such as (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid; phenolic hydroxy group-containing unsaturated monomers such as hydroxystyrene, p-isopropenylphenol, hydroxyphenyl(meth)acrylate, and hydroxyphenyl(meth)acrylamide; and fluorinated hydroxyalkyl group-containing unsaturated monomers such as 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)styrene.

[0023] Examples of the unsaturated monomer (a2) include N-substituted maleimides such as N-arylmaleimide, N-alkylmaleimide, and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and its derivatives; (meth)acrylic acid esters such as (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alicyclic esters, (meth)acrylic acid aromatic ring-containing esters, and (meth)acrylic acid esters having a cyclic ether ring such as an oxirane ring, an oxetane ring, or an oxolane ring; aromatic ring-containing silane compounds such as styryl group-containing silane compounds; vinyl ethers such as alicyclic ring-containing vinyl ethers; and macromonomers having a mono(meth)acryloyl group at the end of a polymer chain such as a polymer chain of an aromatic vinyl compound, a polymer chain of a (meth)acrylic acid ester, or a polysiloxane molecular chain.

[0024] More specific examples of the unsaturated monomers (a1) and (a2) include the monomers described in JP-A-2015-004968, JP-A-2008-233346, and JP-A-2009-229567.

[0025] Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, JP-A-2006-201549, JP-A-2007-128062, JP-A-2008-233563, JP-A-2017-181928, and JP-A-2017-173376.

[0026] In the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2), the copolymerization ratio of the unsaturated monomer (a1) in the copolymer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By using the unsaturated monomer (a1) in such a range, a composition excellent in alkali developability and storage stability can be easily obtained.

[0027] The copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) can be produced by a known method. For example, the structure, weight average molecular weight, and molecular weight distribution can be controlled by the methods disclosed in JP-A-2003-222717, JP-A-2006-259680, WO 2007 / 029871, and the like.

[0028] Furthermore, as the component (A), for example, as disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095, etc., a carboxy group-containing polymer having a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth)acryloyl group) in a side chain can also be used.

[0029] Further examples of component (A) include alkali-soluble polysiloxanes, cardo resins, polyimides, and polybenzoxazoles.

[0030] Specific examples of alkali-soluble polysiloxanes include copolymers disclosed in WO 2017 / 188047, WO 2017 / 169763, WO 2017 / 159876, JP 2020-184010 A, JP 2013-114238 A, JP 2012-53381 A, and JP 2010-32977 A. The alkali-soluble polysiloxane is preferably a silsesquioxane having a first structural unit represented by the following formula (4) and a second structural unit represented by the following formula (5).

[0031] [ka] (In formula (4), X is a monovalent organic group having an unsaturated double bond. In formula (5), Y is a monovalent organic group having a carboxy group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof.)

[0032] In formula (4), X is preferably a group represented by the following formula (6). In formula (5), Y is preferably a group represented by the following formula (7a) or formula (7b).

[0033] [ka]

[0034] In formula (6), formula (7a) and formula (7b), R 7 Each of R is independently a hydrogen atom or a methyl group. 8 R is independently an alkanediyl group having 2 to 10 carbon atoms. 9 R is a divalent organic group. 10 is a single bond or a divalent organic group. Each Z is independently a sulfur atom. * indicates a bonding site.

[0035] The alkali-soluble cardo resin is not particularly limited as long as it is a resin that can be dissolved in an alkaline developer, but is preferably a resin containing one or more anionic groups such as a carboxy group, a sulfonic acid group, or a phosphonic acid group. A cardo resin is a resin having a cardo skeleton, which is a skeleton in which two aromatic groups are bonded by single bonds to one carbon atom constituting a cyclic structure.

[0036] The cardo resin is preferably a radically polymerizable resin, and can be obtained, for example, by reacting a cardo structure-containing epoxy resin with at least one compound having an acidic group selected from (meth)acrylic acid, dicarboxylic acid anhydrides, tetracarboxylic acid dianhydrides, etc. Commercially available radically polymerizable cardo resins include, for example, "WR-301" manufactured by ADEKA CORPORATION; "V-259ME" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "Oxol CR-TR1," "Oxol CR-TR2," "Oxol CR-TR3," "Oxol CR-TR4," "Oxol CR-TR5," and "Oxol CR-TR6" manufactured by Osaka Gas Chemical Co., Ltd.

[0037] From the viewpoint of alkali developability, the acid value of the alkali-soluble cardo resin is preferably from 10 mgKOH / g to 300 mgKOH / g, and more preferably from 20 mgKOH / g to 200 mgKOH / g.

[0038] Specific examples of alkali-soluble polyimides or polybenzoxazoles include copolymers disclosed in WO 2017 / 169763, WO 2017 / 159876, WO 2017 / 057281, WO 2017 / 159476, WO 2017 / 073481, WO 2017 / 038828, WO 2016 / 148176, JP 2015-114355 A, JP 2013-164432 A, JP 2010-72143 A, and the like.

[0039] The weight average molecular weight (Mw) of the component (A) as determined by gel permeation chromatography (GPC) is preferably from 1,000 to 100,000, and more preferably from 3,000 to 50,000. The ratio (Mw / Mn) of Mw to number average molecular weight (Mn) of the component (A) is preferably 1.0 to 10.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 3.0. Specifically, Mw and Mn are polystyrene equivalent values ​​measured by the method described in the Examples below.

[0040] The content of component (A) in the present composition is preferably 10% by mass or more, more preferably 15% by mass or more, relative to 100% by mass of the solid content of the present composition (i.e., all components other than the solvent in the present composition), and is preferably 90% by mass or less, more preferably 85% by mass or less. When the content of the component (A) is within the above range, a composition that has excellent alkali developability and storage stability can be easily obtained, and a cured product that has excellent light-blocking properties can be easily formed.

[0041] [Component (B): Polymerizable compound (B)] The component (B) is essential for forming a cured product of the present composition, and although there is no particular limitation, it is preferably a compound having a polymerizable carbon-carbon unsaturated bond. The (B) component may be any polymerizable compound other than the (A) component, and examples thereof include (meth)acryloyl group-containing compounds, linear vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Among these, (meth)acryloyl group-containing compounds are preferred.

[0042] The component (B) may be either a monofunctional compound or a polyfunctional compound, and a monofunctional compound and a polyfunctional compound may be used in combination as the component (B).

[0043] Specific examples of the (B) component being a monofunctional compound include (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Among these, (meth)acryloyl group-containing compounds are preferred, and (meth)acryloyl group-containing compounds that are at least one selected from the group consisting of (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure are more preferred.

[0044] Specific examples of the compound include (meth)acrylic acid esters having a chain structure, such as (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, and (meth)acrylic acid polyoxyalkylene esters.

[0045] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0046] Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0047] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate.

[0048] Examples of (meth)acrylic acid polyoxyalkylene esters include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, and 2-ethylhexyloxydiethylene glycol (meth)acrylate.

[0049] Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ]decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ]Decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0050] Examples of the (meth)acrylic acid ester having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, and (1,1'-biphenyl-4-yl)methyl (meth)acrylate.

[0051] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0052] Examples of the chain vinyl compound include propene, butene, pentene, and hexene.

[0053] Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, and vinylnaphthalene.

[0054] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0055] Specific examples of when the component (B) is a polyfunctional compound include polyfunctional (meth)acrylic acid esters, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds. Examples of the polyfunctional (meth)acrylic acid ester include bifunctional (meth)acrylic acid esters, trifunctional or higher (meth)acrylic acid esters, etc. Specific examples of these include bifunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol F ethoxylate di(meth)acrylate, cresol novolac ethoxylate di(meth)acrylate, and biphenyl ethoxylate di(meth)acrylate.

[0056] Examples of the trifunctional or higher (meth)acrylic acid ester include trimethylolpropane tri(meth)acrylate, trimethylolpropane polypropylene glycol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide oligomer modified dipentaerythritol hexa(meth)acrylate (e.g., diethylene glycol modified dipentaerythritol hexa(meth)acrylate). tris(meth)acrylate), tris(2-(meth)acryloyloxyethyl)phosphate, succinic acid modified pentaerythritol tri(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, a carboxy group-containing polybasic acid modified (meth)acrylic oligomer, and a polyfunctional urethane acrylate compound obtained using a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxy groups in the molecule and having three, four or five (meth)acryloyloxy groups.

[0057] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0058] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0059] The content of component (B) in the present composition is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 70% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the solid content of the present composition. When the content of the component (B) is within the above range, a photosensitive composition exhibiting good sensitivity, resolution and solvent resistance can be easily obtained.

[0060] [Component (C): Photopolymerization initiator (C)] Although there is no particular limitation on the component (C), a photoradical polymerization initiator that generates radicals in response to radiation and can initiate polymerization is preferred. Examples of the component (C) include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0061] Examples of the O-acyloxime compounds include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octan-1-one oxime-O-acetate, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo

[0113] 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-1-(O-acetyloxime), 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-1-(O-acetyloxime), fluorene skeleton-containing O-acyloxime compounds represented by the following formulas (C-1) and (C-2), and diphenylsulfide skeleton-containing O-acyloxime compounds represented by the following formula (C-3).

[0062] [ka]

[0063] Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

[0064] Specific examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0065] Specific examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone.

[0066] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0067] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0068] As the component (C), an O-acyloxime compound is preferable, and from the viewpoint of improving the contrast ratio of the cured film, an O-acyloxime compound having a diphenyl sulfide skeleton, an O-acyloxime compound having a carbazole skeleton, or an O-acyloxime compound having a fluorene skeleton is more preferable, and an O-acyloxime compound having a diphenyl sulfide skeleton, or an O-acyloxime compound having a fluorene skeleton is even more preferable.

[0069] As the component (C), a photoradical polymerization initiator may be used alone or in combination with a photoacid generator that generates cations in response to radiation or a photobase generator that generates anions in response to radiation. When a photoacid generator or a photobase generator is used in combination as the component (C), the content of the photoradical polymerization initiator is preferably 20 mass % or more, more preferably 30 mass % or more, and even more preferably 40 mass % or more, based on the total amount of the component (C) used, from the viewpoint that the heat resistance and solvent resistance of the obtained cured film can be further improved,

[0070] The content of component (C) in the present composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less, based on 100 mass% of the solid content of the present composition. When the content of component (C) is within the above range, a photosensitive composition exhibiting good sensitivity, resolution and solvent resistance can be easily obtained.

[0071] [Component (D): Compound (D) represented by formula (1)] Component (D) is a compound having a γ-lactam ring represented by the following formula (1) (hereinafter also referred to as "compound (1)") and can be used as a black colorant. Component (D) has excellent solubility in solvents at room temperature, so it is classified as a "dye" among colorants.

[0072] [ka] [In formula (1), R 1 and R 2 are each independently a hydrogen atom or a leaving group, R 1 and R 2 at least one of is a leaving group, R 3 and R 4 each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2 are each independently an integer of 0 to 4.

[0073] In this specification, a "leaving group" refers to a group that is eliminated by heat, light, etc. and is replaced with a hydrogen atom. In other words, component (D) is a component from which the elimination group is eliminated by heat, light, etc., to form a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"). The leaving group in component (D) is preferably a group that is eliminated by heat and replaced with a hydrogen atom (hereinafter also referred to as a "thermally eliminable group"), more preferably a thermally eliminable group that is eliminated at a heating temperature of 250°C or less, even more preferably a thermally eliminable group that is eliminated at a heating temperature of 230°C or less, and particularly preferably a thermally eliminable group that is eliminated at a heating temperature of 200°C or less.

[0074] Examples of the leaving group include a methoxymethyl group (MOM group), an alkyloxycarbonyl group having a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyloxycarbonyl group having a linear or branched alkenyl group having 1 to 10 carbon atoms, and an oxycarbonyl group having a cyclic structure having 1 to 20 carbon atoms. These groups may be partially substituted with at least one atom selected from a silicon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom, and the alkyl group or alkenyl group may have an alkoxy group having 1 to 3 carbon atoms. More specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, an allyloxycarbonyl group, an n-butoxycarbonyl group, an isobutyloxycarbonyl group, a tert-butoxycarbonyl group (Boc group), an n-pentyloxycarbonyl group, a 2-methoxyethyloxycarbonyl group, a heptyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an octyloxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 2-(trimethylsilyl)ethoxycarbonyl group, and a 9-fluorenylmethyloxycarbonyl group (F-moc group).

[0075] Among these, a methoxymethyl group and a tert-butoxycarbonyl group are preferred because they have excellent solubility in a solvent and can easily give compound (1) from which the leaving group is eliminated by heating at a low temperature (e.g., 200°C).

[0076] In the formula (1), R 1 and R 2 is preferably the above-mentioned leaving group, and more preferably a thermally leaving group, from the viewpoint that compound (1) having excellent solubility in a solvent can be easily obtained.

[0077] In the formula (1), R 3 and R 4 are each preferably independently a chlorine atom or an organic group. The organic group is preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group.

[0078] In the formula (1), n 1 and n 2 are each independently preferably 0 to 2, and more preferably 0. 1 or n 2 When is an integer of 1 or more, that is, when the dihydroindolone ring in compound (1) has substituents at positions 4 to 7, it is preferable that the dihydroindolone ring has a substituent at position 4 or 6 in terms of ease of production, availability, etc.

[0079] Compound (1) has geometric isomers of EE, ZZ and EZ isomers, and may be any one of these compounds or a mixture of these geometric isomers.

[0080] Compound (1) can be synthesized, for example, by synthesizing compound (2) by the method described in International Publication No. 2000 / 24736, and then protecting the amine in the dihydroindolone ring of compound (2) by a known amine protection method or alcohol protection method. Compound (2) may be a commercially available product.

[0081] Compound (1) can be prepared by reacting isatin with a compound serving as a raw material for the leaving group, such as a dialkyl dicarbonate, a dialkenyl dicarbonate, a dialkoxyalkyl dicarbonate, an alkyl chlorocarboxylic acid, an alkenyl chlorocarboxylic acid, or a chlorocarboxylic acid having a cyclic structure, in the presence of a base, such as pyridine or 4-dimethylaminopyridine, to obtain a compound having a leaving group bonded to the nitrogen atom of isatin, such as N-carbonyloxyalkylisatin, and then reacting the compound with the nitrogen atom of isatin, such as N-carbonyloxyalkylisatin, in the presence of a base, such as pyridine or 4-dimethylaminopyridine, to obtain a compound having a leaving group bonded to the nitrogen atom of is ... such as N-carbonyloxyalkylisatin, and then reacting the compound with the nitrogen atom of isatin, as described in JP 2016-84425 A, JP 2015-121753 A, WO 2014 / 071524 A, J. Am. Chem. Soc., 2013, 135, 12168., J. Am. Chem. Soc., 2015, 137, It can also be obtained by reacting with 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione in the presence of an acid or base catalyst, as described in, for example, US Pat. No. 15947.

[0082] Examples of the acid catalyst include organic carboxylic acids such as hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, paratoluenesulfonic acid, and benzoic acid, and examples of the base catalyst include organic amines such as n-butyllithium, lithium diisopropylamide, and triethylamine, organic bases such as pyridines, and inorganic bases such as sodium hydride, sodium hydroxide, and potassium carbonate. The isatin can be synthesized, for example, by condensing chloral hydrate, aniline, and hydroxylamine in sulfuric acid. However, it is also possible to synthesize isatin by using aniline having an organic group such as an alkyl group or an alkoxy group instead of unsubstituted aniline, so that R of compound (1) can be obtained. 3 and / or R 4 The aggregation property and solubility can be adjusted by introducing an organic group into the compound (1). The aggregation property and solubility can also be adjusted by mixing a plurality of compounds (1) having asymmetric structures or different structures.

[0083] [ka] [In formula (2), R 3 , R 4 , n 1 and n 2each independently has the same meaning as the corresponding symbol in formula (1).

[0084] Compound (2) is a compound generally known as a lactam pigment and is used as a black pigment, and a cured film containing compound (2) has excellent light-shielding properties. Therefore, a cured material containing compound (2) produced by elimination of a leaving group from compound (1) has excellent light-shielding properties. In addition, compound (2) is classified as a "pigment" among colorants because of its poor solubility in solvents at room temperature. Due to its low solubility, a cured product containing compound (2) as a colorant can suppress dissolution (migration) into a light-emitting layer, etc., during use of the cured product.

[0085] The content of component (D) in the present composition is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 12 mass% or more, relative to 100 mass% of the solid content of the present composition, and is preferably 60 mass% or less, more preferably 55 mass% or less, and even more preferably 30 mass% or less. When the content of the (D) component is within the above range, the radiation (particularly g-rays, h-rays, and i-rays) transmittance is excellent, so that a photosensitive composition with excellent sensitivity can be easily obtained, and a cured product with excellent light-shielding properties can be easily formed.

[0086] [Other ingredients] In addition to the above-mentioned components (A) to (D), the present composition may further contain other components (hereinafter also referred to as "other components") within the scope that does not impair the effects of the present invention. Examples of such other components include solvents, colorants other than component (D), dispersants, dispersing aids, surfactants, polymers other than components (A) and (B), polymerization inhibitors, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, and ultraviolet absorbers. The blending ratio of these other components is appropriately selected depending on each component within a range that does not impair the effects of the present invention.

[0087] ·solvent The present composition is preferably a liquid composition in which the components (A) to (D) and other components that are blended as necessary are dissolved or dispersed in a solvent (hereinafter also referred to as "solvent (E)"). As the solvent (E), an organic solvent that dissolves each component blended in the present composition and does not react with each component is preferable.

[0088] Specific examples of the solvent (E) include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ketoalcohols such as diacetone alcohol; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0089] Since the present composition contains the component (D), the solvent (E) is preferably a mixed solvent containing the following first and second solvents. First solvent: at least one selected from the group consisting of esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; and ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether. Second solvent: at least one selected from the group consisting of amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and ketoalcohols such as diacetone alcohol.

[0090] The compound (1) which is the component (D) tends to have particularly high solubility in the second solvent. More specifically, the compound (1) usually has a solubility in the second solvent at 25° C. of 10 mass % or more.

[0091] When a mixed solvent of the first and second solvents is used as the solvent (E), the content of the second solvent is preferably 30% by mass or more, more preferably 40% by mass or more, based on the total amount of solvent in the composition, in order to ensure sufficient solubility of the component (D) in the solvent, etc. Also, in terms of the solubility and coatability of each component, the content of the second solvent is preferably 95% by mass or less, more preferably 90% by mass or less.

[0092] When a solvent (E) is blended with the present composition, it is preferable to use the solvent (E) so that the solids concentration of the present composition falls within the following range, from the standpoints of the solubility and dispersibility of the components (A) to (D) and the coatability of the present composition when it is applied to a substrate.

[0093] Coloring agents other than component (D) In the present composition, only the component (D) may be used as the colorant; however, the use of a colorant other than the component (D) tends to improve the light-blocking properties of the cured product obtained from the present composition. Examples of colorants include organic pigments such as lactam pigments, benzofuranone pigments, azo pigments, and perylene pigments; inorganic pigments such as carbon black and titanium black; and dyes other than component (D).

[0094] Examples of dyes other than the component (D) include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, and leuco dyes.

[0095] When a colorant other than the component (D) is blended in the present composition, from the viewpoints of easily obtaining a composition having excellent sensitivity, developability, and radiation (particularly, g-rays, h-rays, and i-rays) transmittance, and easily forming a cured product having excellent light-shielding properties, the blending amount of the colorant other than the component (D) is preferably 0.1 mass % or more, more preferably 1 mass % or more, and preferably 30 mass % or less, and more preferably 20 mass % or less, relative to 100 mass % of the solid content of the present composition. Furthermore, from the viewpoint of being able to easily obtain a composition that is excellent in sensitivity, developability, and radiation (particularly g-rays, h-rays, and i-rays) transmittance, it is preferable that the amount of colorants other than component (D) contained in the present composition be as small as possible, and therefore it is also preferable that the composition does not contain any colorants other than component (D).

[0096] When a pigment is used as a colorant other than component (D), the form in which it is used is not particularly limited, and it may be used as a powder or a dispersion. Among these, it is preferable to prepare the composition of the present invention by making the pigment into a master batch and using the pigment master batch dispersion in terms of solvent solubility, solvent dispersibility, etc. It is preferable to use a resin for the pigment master batch, and the resin is not particularly limited, but is preferably the same resin as component (A). It is preferable to mix a dispersant described later in the pigment master batch to improve dispersibility.

[0097] Examples of the dispersion medium in the pigment masterbatch dispersion liquid include organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether propionate, and propylene glycol monomethyl ether; and water.

[0098] Dispersants When a pigment is used as a colorant other than component (D), it is preferable to use a dispersant because it is preferable to finely disperse the pigment and stabilize the dispersed state from the viewpoint of the stability of the quality of the composition. A dispersing aid may also be used together with the dispersant. Even when a pigment is not used, if the solubility of component (D) is poor, a dispersant can be used to maintain a stable dispersed state.

[0099] As the dispersant, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, etc., a polymer dispersant having a functional group such as a carboxy group, a phosphoric acid group, a sulfonic acid group, a base thereof, a primary, secondary or tertiary amino group, a quaternary ammonium base, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is preferred. Among these, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group, a quaternary ammonium base, or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferred because it is possible to disperse the pigment with the use of a small amount of dispersant.

[0100] Examples of polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants obtained using a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.

[0101] When a pigment and a dispersant are blended in the composition, the amount of the dispersant blended is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of the pigment. When no pigment is used in the composition and a dispersant is blended in, the amount of the dispersant blended is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of component (D). From the viewpoints of ease of production of the present composition, production costs, and the like, it is preferable that the amount of other components that may be contained in the present composition is as small as possible. Also, since gases and the like caused by dispersants may be generated from the cured film, it is also preferable that the composition does not contain a dispersant.

[0102] Dispersion aid When a dispersant is used in the present composition, a dispersing aid may be used together with the dispersant. The dispersion aid may, for example, be a pigment derivative. Examples of the pigment in the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, and diketopyrrolopyrrole-based pigments. Examples of pigment derivatives include compounds in which a sulfonic acid group, a sulfonamide group, a quaternary salt of a sulfonamide group, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, or the like is bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, or the like.

[0103] Surfactants For example, the use of a surfactant in the composition can improve the coatability of the composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

[0104] As the fluorine-based surfactant, commercially available products may be used, and examples of the commercially available products include Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); F-top EF301, EF303, and EF352 (manufactured by Shin-Akita Chemical Co., Ltd.).

[0105] As the silicone surfactant, commercially available products may be used, and examples of the commercially available products include SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, and L-7002 (manufactured by Dow Toray Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, 306, 310, 330, 335, 341, 344, 370, 340, and 345 (manufactured by BYK Japan Co., Ltd.).

[0106] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0107] When a surfactant is added to the present composition, the amount of the surfactant added is preferably 0.01 to 1.5 mass%, more preferably 0.02 to 1.2 mass%, and even more preferably 0.05 to 1.0 mass%, relative to 100 mass% of the solid content of the present composition.

[0108] Antioxidants For example, by using an antioxidant, degradation due to cleavage of polymer molecules in the present composition can be suppressed, and durability and the like can be improved. Examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0109] When an antioxidant is blended in the present composition, the blending amount of the antioxidant is preferably 0.01 to 1.5 mass%, more preferably 0.02 to 1.2 mass%, and even more preferably 0.05 to 1.0 mass%, relative to 100 mass% of the solid content of the present composition.

[0110] Adhesion assistant Use of the present composition containing an adhesion aid can improve the adhesion between the formed cured product and a substrate (adherend), thereby preventing the cured product from peeling off from the substrate during a development process or the like. The adhesion aid may be a functional silane coupling agent having a reactive functional group. Examples of the reactive functional group contained in the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0111] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0112] When an adhesion aid is blended in the present composition, the blending amount is preferably 0.01 to 4.0 mass %, more preferably 0.1 to 4.0 mass %, relative to 100 mass % of the solid content of the present composition.

[0113] [Method of preparing the composition] The composition can be prepared, for example, by uniformly stirring and mixing the components (A) to (D) and any other components that may be added, and dissolving or dispersing them uniformly. The components can be mixed using a known mixer such as a roll mill, ball mill, or sand mill. After mixing the components, the resulting mixture may be filtered, for example, through a filter having a pore size of 2 μm or less, if necessary.

[0114] The solid content concentration of the composition (i.e., the ratio of the total mass of the components other than the solvent in the composition to the total mass of the composition) is appropriately selected in consideration of viscosity, volatility, etc. The solid content concentration of the composition is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, and even more preferably 5 to 40 mass%. If the solid content concentration is equal to or higher than the lower limit, it is preferable in that a sufficient thickness of the coating film can be ensured when the composition is applied to a substrate (adherend). On the other hand, if the solid content concentration is equal to or lower than the upper limit, it is preferable in that the viscosity of the composition can be appropriately increased and good coatability can be ensured.

[0115] The present composition can be suitably used for forming cured products having light-shielding properties, such as black matrices and black banks used in color filters, etc. Cured products obtained from the present composition, particularly black matrices and black banks having excellent light-shielding properties, are particularly useful for liquid crystal display elements, solid-state imaging elements, color sensors, organic EL display elements, electronic paper, etc.

[0116] ≪Cured product≫ The cured product of the present disclosure (hereinafter also referred to as the "present cured product") is a cured product of the present composition, and specifically, is formed by irradiating the present composition with radiation. The present cured product can be formed into a desired shape, for example, by controlling the shape of the coating film when the present composition is applied, or by combining site-selective exposure and development.

[0117] The present cured product is particularly preferably used as a black matrix or black bank in color filters and the like used in various image display devices. The black material that separates the red, green, and blue (RGB) cells in color filters is called a black matrix. Also, partition walls are formed on a substrate, and organic EL light-emitting layers are formed in the recessed spaces defined by the partition walls using an inkjet method or other methods. The partition walls that are blackened to prevent light leakage between pixels are called black banks. A color filter having a black matrix made of a cured product formed using the present composition is preferably used in an image display panel. The image display panel is preferably used in various image display devices such as liquid crystal display devices and organic EL display devices. It is also preferably used in a touch panel having both an image display panel and a surface sensor made of a capacitance electrode, a resistance electrode, or the like.

[0118] [Method of manufacturing the cured product] The method for producing the present cured product includes a step of irradiating the present composition with radiation. When irradiating with radiation, the radiation may be selectively irradiated at a position using a mask having a predetermined pattern, if necessary. Development may be carried out after the radiation exposure, and / or a heat treatment may be carried out after the radiation exposure.

[0119] The present composition is particularly suitable as a negative pattern-forming material formed by exposing a portion of an organic film formed from the present composition to light and dissolving the unexposed portion of the exposed organic film in an alkaline developer.

[0120] Suitable examples of the method for producing the present cured product include the following first and second production methods.

[0121] <First manufacturing method> The first production method is a method including the following steps (I) to (IV) and may further include the following step (V) as necessary.

[0122] (Process (I): Coating process) Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition onto the substrate.

[0123] Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates having colored resists, overcoats, anti-reflection films, various metal thin films, sealing films, etc. formed on their surfaces. Examples of the plastic substrate include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. The substrate may be provided in advance with various elements (for example, a light receiving element such as a photodiode, or a light emitting element such as an organic light emitting diode).

[0124] The composition can be applied by any suitable method, such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, inkjet coating, etc. Of these, spin coating, bar coating, and slit die coating are preferred.

[0125] After the composition is applied onto a substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping, etc. The prebaking conditions can be appropriately set depending on the types and usage ratios of each component used in the composition, and can be, for example, at 60 to 130° C. for about 30 seconds to 10 minutes. The pre-baking is preferably performed at a temperature at which the leaving groups in the component (D) do not leave.

[0126] The thickness of the coating film formed after prebaking is preferably 0.2 μm or more, more preferably 0.3 to 5 μm, and even more preferably 0.4 to 3 μm.

[0127] (Step (II): Exposure step) Step (II) is a step of position-selectively irradiating the coating film formed in step (I) with radiation. This radiation exposure causes a curing reaction to proceed in the exposed areas, resulting in a cured product in which the exposed areas are cured. In step (II), the site-selective irradiation of the coating film is usually carried out through a mask having a pattern for obtaining a cured product having a desired shape. The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0128] Examples of the radiation to be irradiated onto the coating film include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Examples of ultraviolet rays include g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). X-rays include, for example, synchrotron radiation. An example of the charged particle beam is an electron beam. Of these, ultraviolet rays are preferred, and ultraviolet rays including g-rays, h-rays and i-rays are more preferred. Examples of light sources used for radiation irradiation include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and LED lamps. The radiation exposure is 100 to 50,000 J / m 2 (10~5,000mJ / cm 2 ) is preferable, and 100 to 6,000 J / m 2 (10~600mJ / cm 2 ) is more preferred.

[0129] (Process (III): Development process) Step (III) is a step of forming a pattern on the substrate by developing the coating film and the cured product obtained in step (II). This development step removes the coating film formed on the substrate in the unexposed areas, and a cured product in the exposed areas (e.g., linear cured product) remains, forming a patterned cured product (e.g., a concave-convex pattern formed by a number of regularly arranged linear cured products) on the substrate.

[0130] The developer may be an aqueous solution of an alkali (basic compound). Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. The aqueous alkali solution may contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or may contain a small amount of any of various organic solvents capable of dissolving the present composition.

[0131] The concentration of the developer can be appropriately determined depending on the composition of the composition, but is usually from 0.01 to 10% by mass, preferably from 0.5 to 5% by mass.

[0132] As the developing method, for example, a puddle method, a dipping method, a swing immersion method, a shower method, or other suitable method can be used. The developing time may be appropriately adjusted depending on the composition of the present composition, and is, for example, 20 to 120 seconds.

[0133] After the development step, a step of washing the developed patterned substrate with pure water or the like may be carried out, if necessary. In addition, a step of drying the patterned substrate after development or after the cleaning may be carried out. The conditions for the drying are not particularly limited, but may be, for example, the same conditions as those for the pre-baking.

[0134] This composition has excellent transmittance to ultraviolet rays (especially g-rays, h-rays and i-rays) and therefore has excellent sensitivity during exposure. Therefore, the patterned cured product obtained from this composition adheres well to the substrate and can also form patterns with narrow line widths.

[0135] (Step (IV): Post-baking step) Step (IV) is a step of heating the developed pattern to eliminate the leaving group from the component (D) in the patterned cured product. Step (IV) may also be a step of removing the solvent and moisture in the patterned cured product, further curing the composition by thermal crosslinking, and improving adhesion to the substrate and corrosion resistance.

[0136] The heat treatment can be carried out, for example, using a heating device such as an oven or a hot plate, and may be carried out in any environment, such as under a nitrogen atmosphere or under air. The heating temperature in step (IV) may be appropriately selected depending on the base material and the present composition used, but is preferably a temperature equal to or higher than the temperature at which the leaving group is eliminated from component (D), and although depending on the type of leaving group, a temperature of 150 to 270°C is more preferable, and 180 to 230°C is even more preferable. The heating time can be appropriately set depending on the type of heating device, etc. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. When heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In the step (IV), a step bake method in which heat treatment is performed multiple times can also be used.

[0137] (Step (V): Post-exposure step) Step (V) is a step of further irradiating the cured product obtained after development in step (III) and / or the cured product obtained in step (IV) with radiation. Among these, the step of further irradiating the cured product obtained in step (IV) with radiation is preferred from the viewpoint of easily forming a cured product in a desired shape, etc. By irradiating with radiation in step (V) (hereinafter also referred to as "post-exposure"), the heat resistance, chemical resistance, etc. can be further improved, and a highly reliable cured product can be easily formed. Among these, the type of radiation and the exposure conditions in the post-exposure can be the same as those in step (II). Note that the conditions such as the wavelength and dose of the irradiated light and the light source in the post-exposure may be the same as or different from those in step (II).

[0138] <Second manufacturing method> The second manufacturing method includes a step of forming a pattern by inkjet coating the present composition on a substrate. In the second manufacturing method, a pattern of a desired shape may be directly formed on the substrate by inkjet coating, and then the same step (IV) as in the first manufacturing method may be performed to form a desired cured product. The second production method may include a step similar to step (V) in the first production method.

[0139] Image display device The image display device of the present disclosure is not particularly limited as long as it contains the present cured product, and may have any conventionally known configuration other than the inclusion of the present cured product. Examples of the image display device include liquid crystal displays (LCDs), organic ELs using organic light emitting diodes (OLEDs), μLED displays, electrochromic displays (ECDs), electroluminescent displays (ELDs), and displays using quantum dot-organic EL (QD-OLEDs).

[0140] ≪Compound≫ The compound of the present disclosure is a compound represented by the following formula (3) (hereinafter also referred to as "compound (3)"). Such compound (3) has excellent solubility in solvents at room temperature. By using such compound (3), a photosensitive composition having excellent sensitivity and developability as well as a cured product having excellent light-shielding properties can be easily formed.

[0141] [ka] [In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally labile group which is eliminated at a heating temperature of 250° C. or less, and R 5 and R 6 at least one of the groups is the thermally detachable group, R3 and R 4 each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2 are each independently an integer of 0 to 4.

[0142] In the above formula, R 3 , R 4 , n 1 and n 2 have the same meanings as the same symbols in formula (1) above.

[0143] In the above formula, R 5 and R 6 is preferably the above-mentioned thermally eliminable group, since it is possible to easily obtain a compound (3) having excellent solubility in a solvent. The thermally detachable group is more preferably a thermally detachable group which is desorbed at a heating temperature of 230° C. or less, and further preferably a thermally detachable group which is desorbed at a heating temperature of 200° C. or less. Examples of the thermally detachable group that is detached at a heating temperature of 200° C. or less include a methoxymethyl group (MOM group) and a tert-butoxycarbonyl group (Boc group).

[0144] Preferred specific examples of compound (3) include structures represented by the following formulae, but are not limited thereto.

[0145] [ka]

[0146] At room temperature, compound (3) dissolves in the second solvent (particularly, ketones such as cyclohexanone, ketoalcohols such as diacetone alcohol, and amides such as N-methylpyrrolidone) to a concentration of preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. When the solvent solubility is equal to or more than the lower limit, it can be said that the compound (3) has excellent solubility in the solvent (E), particularly in ketones, ketoalcohols, and amides. By using the compound (3), a photosensitive composition having excellent sensitivity and developability can be easily obtained.

[0147] Compound (3) can be produced by the same method as for compound (1), for example, the methods described in Synthesis Examples 1 and 2 in the Examples below. EXAMPLES

[0148] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0149] [Synthesis Example 1] Synthesis of lactam dye (compound (D-1)) In a reaction vessel equipped with a cooling tube, 2.00 g of lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] was added to 10.00 g of N-methylpyrrolidone and dispersed. Then, 1.95 g of di-tert-butyl dicarbonate, 0.11 g of 4-dimethylaminopyridine, and 1.32 g of triethyl orthoformate were added. The resulting solution was heated to 50° C. under a nitrogen stream while stirring and stirred for 5 hours. Then, the resulting reaction solution was cooled to room temperature and then dropped into 200 mL of hexane. The resulting precipitate was collected by filtration and dissolved in 200 mL of dichloromethane. The resulting dichloromethane solution was washed three times with 200 mL of ion-exchanged water, and the organic layer was concentrated under reduced pressure using a rotary evaporator, and then dried under reduced pressure at room temperature to obtain the desired Bk-dye-1 (hereinafter also referred to as "compound (D-1)").

[0150] [ka]

[0151] [Synthesis Example 2] Synthesis of lactam dye (compound (D-2)) In a reaction vessel equipped with a cooling tube, 2.00 g of lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] was added to 10.00 g of N,N-dimethylformamide and dispersed. Then, 0.79 g of chloromethyl methyl ether and 0.21 g of sodium hydride were added, and the resulting solution was heated to 40° C. under a nitrogen stream while stirring, and stirred for 16 hours. Then, the resulting reaction solution was cooled to room temperature, and 40 mL of saturated aqueous sodium bicarbonate solution was added, and the mixture was stirred for 1 hour. The resulting liquid was extracted three times with 100 mL of dichloromethane. The dichloromethane solution after the three extractions was washed three times with 200 mL of ion-exchanged water, and the organic layer was concentrated under reduced pressure using a rotary evaporator, and then dried under reduced pressure at room temperature to obtain the desired Bk-dye-2 (hereinafter also referred to as "compound (D-2)").

[0152] [ka]

[0153] [Synthesis Example 3] Synthesis of lactam dye (compound (D-3)) In a reaction vessel equipped with a cooling tube, 5 g of isatin and 7.5 g of 2-ethylhexyl chloroformate were dissolved in 100 mL of benzene. Then, 10 g of pyridine was added and stirred at 50°C for 5 hours. The reaction solution was then concentrated under reduced pressure using a rotary evaporator, and dissolved in 200 mL of ethyl acetate. This ethyl acetate solution was washed three times with 200 mL of ion-exchanged water, and the organic layer was concentrated under reduced pressure using a rotary evaporator, and then dried under reduced pressure at room temperature to obtain the desired 2EH-isatin.

[0154] [ka]

[0155] In a reaction vessel equipped with a cooling tube, 3.3 g of 2EH-isatin and 0.95 g of 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione were dispersed in 100 mL of acetic acid. Then, 0.5 g of p-toluenesulfonic acid monohydrate was added and stirred at 115°C for 11 hours. After the obtained reaction solution was cooled to room temperature, the reaction solution was poured into 500 mL of isopropanol. Then, a precipitate was obtained by filtration and further washed twice with 50 mL of isopropanol. The obtained solid was dried under reduced pressure to obtain the target Bk-dye-3 (hereinafter also referred to as "compound (D-3)").

[0156] [ka]

[0157] [Synthesis Example 4] Synthesis of alkali-soluble polymer (A-1) In a flask equipped with a cooling tube and a stirrer, 3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of a solvent in which equal amounts of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone were mixed were charged. Into this flask, 12 parts by mass of N-cyclohexylmaleimide, 10 parts by mass of styrene, 20 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate, 14 parts by mass of benzyl methacrylate, and 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) were charged and substituted with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80°C by gentle stirring, and this temperature was maintained for 3 hours to polymerize. The temperature of the reaction solution was then raised to 100°C, and polymerization was continued for another hour to obtain an alkali-soluble polymer solution containing 33.3% by mass of a poly(meth)acrylic resin (hereinafter also referred to as "alkali-soluble polymer (A-1)"). The alkali-soluble polymer (A-1) had an Mw of 9,700 and an Mn of 5,700.

[0158] [Synthesis Example 5] Synthesis of alkali-soluble polymer (A-2) (a resin having acryloyl and carboxyl groups obtained by modifying cresol novolac type epoxy acrylate resin with acid anhydride) 220 parts by mass of cresol novolac epoxy resin (manufactured by DIC Corporation, product name: Epicron N-695, epoxy equivalent: 220 g / eq.) was placed in a four-neck flask equipped with a stirrer and a reflux condenser, and 214 parts by mass of propylene glycol monomethyl ether acetate was added and dissolved by heating. Next, 0.1 parts by mass of hydroquinone as a polymerization inhibitor and 2.0 parts by mass of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105°C, and 72 parts by mass of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80-90°C, 106 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. After cooling, the mixture was taken out, and an alkali-soluble polymer solution containing a resin having an acryloyl group and a carboxy group (hereinafter also referred to as "alkali-soluble polymer (A-2)"), which was obtained by modifying a cresol novolac type epoxy acrylate resin with an acid anhydride, was obtained (solid concentration: 50% by mass). The weight average molecular weight (Mw) of the obtained alkali-soluble polymer (A-2) was about 3,500.

[0159] [Synthesis Example 6] Synthesis of alkali-soluble polymer (A-3) (cage-type siloxane resin) With reference to the examples of JP 2020-184010 A, a cage-type siloxane resin (hereinafter also referred to as "alkali-soluble polymer (A-3)") was polymerized as follows. 15 g (100 mol% in terms of (meth)acryloyl groups) of silsesquioxane (manufactured by Toagosei Co., Ltd., product name: AC-SQ TA-100), 15 g of acetonitrile, and 4.8 g (25 mol%) of 3-mercaptopropionic acid were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube, and then 9.2 g (50 mol%) of triethylamine was slowly added and reacted at 50 ° C. for 2 hours. When the polymer obtained at this point was confirmed using GPC, it was found that the weight average molecular weight was 4,400 and the amount of 3-mercaptopropionic acid remaining in the reaction solution was 0.1 mol% or less, confirming that the Michael addition was proceeding quantitatively. After the reaction was completed, the mixture was transferred to a separatory funnel, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1M hydrochloric acid and three times with 50 mL of water. Next, 40 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the mixture was concentrated to a liquid volume of 40 g, and then 40 g of PGMEA was added again and concentrated. Then, the solid content was adjusted to 50 mass% with PGMEA, and an alkali-soluble polymer solution containing an alkali-soluble polymer (A-3) was obtained. The weight average molecular weight of the obtained alkali-soluble polymer (A-3) was 4,400.

[0160] <Evaluation of weight average molecular weight> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the prepared polymer are values ​​calculated as polystyrene, measured by gel permeation chromatography (GPC) under the following conditions. Column: TSKgelGRCXLII, manufactured by Tosoh Corporation Solvent: Tetrahydrofuran Temperature: 40℃ Pressure: 68kgf / cm 2

[0161] [Preparation Example 1] Preparation of pigment dispersion (Bk-MB-1) As a colorant, 12 parts by mass of lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)], 11.8 parts by mass of BYK-LPN21116 (manufactured by BYK Japan Co., Ltd., solid content concentration 40.0 mass%) as a dispersant in solution, 13.0 parts by mass of alkali-soluble polymer (A-1) in polymer solution (solid content concentration 33.3 mass%) as a binder, and a mixture consisting of 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion liquid (Bk-MB-1) as a colorant.

[0162] [Preparation Example 2] Preparation of pigment dispersion (Bk-MB-2) A mixture of 12 parts by mass of carbon black (TPX1227R, manufactured by Cabot Corporation) as a colorant, 11.8 parts by mass of BYK-LPN21116 (manufactured by BYK Japan Co., Ltd., solid content concentration 40.0% by mass) as a dispersant in the form of a solution, 13.0 parts by mass of an alkali-soluble polymer (A-1) in the form of a polymer solution (solid content concentration 33.3% by mass) as a binder, and 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium was mixed and dispersed for 12 hours using a bead mill to prepare a pigment dispersion (Bk-MB-2) as a colorant.

[0163] Details of the colorants, components (A), (B), (C), and surfactants used in the preparation of the photosensitive compositions in the examples and comparative examples are given below.

[0164] <Coloring agent> D-1: Bk-dye-1 (compound (D-1)) synthesized in Synthesis Example 1 D-2: Bk-dye-2 (compound (D-2)) synthesized in Synthesis Example 2 D-3: Bk-dye-3 (compound (D-3)) synthesized in Synthesis Example 3 Bk-MB-1: Pigment dispersion prepared in Preparation Example 1 Bk-MB-2: Pigment dispersion prepared in Preparation Example 2 ODB-2 (3-dibutylamino-6-methyl-7-anilinofluoran, manufactured by Yamamoto Chemical Industries, Ltd.)

[0165] <Alkali-soluble polymer (A)> A-1: Poly(meth)acrylic resin synthesized in Synthesis Example 4 A-2: A resin having an acryloyl group and a carboxy group, obtained by modifying the cresol novolac type epoxy acrylate resin synthesized in Synthesis Example 5 with an acid anhydride. A-3: Cage-type siloxane resin synthesized in Synthesis Example 6 A-4: ADEKA Corporation's "WR-301" (PGMEA solution with a solid content of 44% by mass), a resin with acryloyl and carboxyl groups, which is a cardo resin modified with an acid anhydride

[0166] <Polymerizable compound (B)> B-1: Dipentaerythritol penta / hexaacrylate (manufactured by Toagosei Co., Ltd., Aronix M-402)

[0167] <Photopolymerization initiator (C)> C-1: An oxime-based photopolymerization initiator represented by the following formula (C-1): C-2: Diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate salt (manufactured by San-Apro Co., Ltd., CPI-100P (photocationic polymerization initiator))

[0168] [ka]

[0169] <Surfactant> F-1: Megafac F-554 (DIC Corporation, fluorosurfactant)

[0170] [Example 1] A photosensitive composition was prepared by mixing 12.0 parts by mass of compound (D-1), 27.0 parts by mass of alkali-soluble polymer (A-1), 5.0 parts by mass of polymerizable compound (B-1), 1.0 part by mass of photopolymerization initiator (C-1), and 0.1 part by mass of surfactant (F-1), and adding equal amounts of propylene glycol monomethyl ether acetate and cyclohexanone so that the solids concentration of the final composition was 17.0% by mass, followed by stirring. The alkali-soluble polymer (A-1) was prepared by using the polymer solution (solid concentration 33.3 mass%) obtained in Synthesis Example 4 so that the amount of the alkali-soluble polymer (A-1) was 27.0 parts by mass. Similarly, in the tests using the alkali-soluble polymer (A-2) or (A-3), the polymer solutions obtained in Synthesis Examples 5 and 6 were used so that the amount of the alkali-soluble polymer (A-2) or (A-3) was the numerical value (amount) shown in Table 1. In the tests using Bk-MB-1 or Bk-MB-2, the pigment dispersions prepared in Preparation Examples 1 and 2 were used so that the amount of solids was the numerical value (amount) shown in Table 1.

[0171] [Examples 2 to 8 and Comparative Examples 1 to 3] Photosensitive compositions were prepared in the same manner as in Example 1, except that the type and amount of each component was changed as shown in Table 1. The numerical values ​​in the columns for each component in Table 1 indicate parts by mass.

[0172] <Evaluation of Photosensitive Composition> The properties of the photosensitive compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 1.

[0173] <Evaluation of light blocking properties (transmittance)> Each of the prepared photosensitive compositions was applied using a spin coater onto a soda glass substrate having a SiO2 film formed on the surface thereof for preventing the elution of sodium ions, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.0 μm. Next, using a Canon Inc. MPA-600FA, the resulting coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm at 35 mJ / cm through a photomask.2 The film was exposed to an exposure of 100 μm. The exposed glass substrate with the coating was then placed on the horizontal rotating table of a spin-shower developer (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. for 60 seconds. The developed substrate was then washed with ultrapure water, air-dried, and post-baked for 30 minutes in a clean oven at 230° C. to form a 2 cm x 4 cm rectangular pattern on the substrate. The transmittance (OD value) of the obtained strip-shaped pattern was measured using an ultraviolet-visible-near infrared spectrophotometer (Shimadzu Corporation, UV-1900i) when light with a wavelength of 500 nm was incident. The evaluation criteria are as follows. A higher OD value indicates a higher light blocking property. (Evaluation Criteria) AA:OD value is 0.5 or more BB:OD value is 0.3 or more and less than 0.5 CC:OD value is less than 0.3

[0174] <Evaluation of developability> Each of the prepared photosensitive compositions was applied onto a soda glass substrate having an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.0 μm. Next, using a Canon Inc. MPA-600FA, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating film through a photomask at 35 mJ / cm2. 2 The film was exposed to an exposure of 100 μm. The glass substrate with the exposed coating was then placed on the horizontal rotating table of a spin-shower developer (AD-2000 model, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. for 60 seconds. The developed substrate was then washed with ultrapure water, air-dried, and post-baked for 30 minutes in a clean oven at 230° C. to form a rectangular hole pattern with rounded corners and dimensions of 5 μm in length and width on the substrate. Platinum was sputtered onto the obtained patterned substrate using a JEC-3000FC (manufactured by JEOL Ltd.), and then the inside of the hole pattern (the portion removed by development) was observed using a scanning electron microscope (S-4300, manufactured by Hitachi Ltd.) to count the number of foreign bodies (dot-like foreign bodies) present there. The evaluation criteria are as follows. Fewer foreign bodies inside the pattern indicate less residue at the time of development, i.e., better developability. (Evaluation Criteria) AA: The number of foreign objects inside the hole pattern is less than 5 BB: The number of foreign objects inside the hole pattern is 5 or more and less than 10. CC: The number of foreign objects inside the hole pattern is 10 or more.

[0175] <Sensitivity evaluation> Each of the prepared photosensitive compositions was applied onto a soda glass substrate having an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.0 μm. Next, using a Canon Inc. MPA-600FA, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was irradiated onto the coating film at 35 mJ / cm through a photomask capable of forming a line pattern with different line widths in 1 μm increments in the range from 1 μm to 50 μm. 2 The film was exposed to an exposure of 100 μm. Thereafter, the exposed glass substrate with the coating was placed on the horizontal rotating table of a spin-shower developer (AD-2000 type, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds. The developed substrate was then washed with ultrapure water and air-dried, and then post-baked for 30 minutes in a clean oven at 230°C to form a line pattern. The obtained substrate with line pattern was observed under an optical microscope to determine the minimum line width at which the line pattern formed had a shape corresponding to the photomask and was free of defects. The narrower the minimum line width, the more sufficient exposure was possible to the substrate side even for narrow lines, and the more a pattern with excellent adhesion to the substrate was formed, indicating high sensitivity during exposure (high transmittance of the photosensitive composition used to radiation (especially g-rays, h-rays, and i-rays)). (Evaluation Criteria) AA: Minimum line width is less than 4μm BB: Minimum line width is 4μm or more and less than 6μm CC: Minimum line width is 6μm or more

[0176] [Table 1]

[0177] <Evaluation of absorbance before and after 230℃ post-bake> The photosensitive composition prepared in Example 1 was applied by a spin coater onto a soda glass substrate having a SiO2 film formed on its surface for preventing sodium ion elution, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.0 μm. Next, using a Canon Inc. MPA-600FA, the resulting coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm at 35 mJ / cm through a photomask. 2 The film was exposed to an exposure of 100 μm. The exposed glass substrate with the coating was then placed on the horizontal rotating table of a spin-shower developer (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.) and paddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. for 60 seconds. The developed substrate was then washed with ultrapure water, air-dried, and further heated on a hot plate at 100° C. for 5 minutes to form a 2 cm x 4 cm rectangular pattern on the substrate. Using an ultraviolet-visible-near infrared spectrophotometer (Shimadzu Corporation, UV-1900i), the ultraviolet-visible absorbance spectra of the obtained strip pattern and the strip pattern after heating at 230°C were measured. The results are shown in Figure 1. In Figure 1, the "protected" spectrum is the spectrum of the strip pattern before heating at 230°C, and the "deprotected" spectrum is the spectrum of the strip pattern after heating at 230°C. When the photosensitive composition of Example 2 containing compound (D-2) was used for measurement, the ultraviolet-visible absorbance spectrum of the strip-shaped pattern before and after post-baking at 230° C. also showed the same behavior as in Fig. 1. The same was true for the other Examples (Example 3 containing compound (D-3) and Examples 4 to 8).

[0178] By introducing a t-butoxycarbonyl group, which is a thermally detachable group, into the lactam represented by the formula (2) as in the compound (D-1), it was possible to reduce the absorbance of radiation (i-rays, h-rays) (increase the transmittance) as shown in "protection" in FIG. 1. For this reason, it is considered that the sensitivity was increased in Example 1 using the compound (D-1) compared to Comparative Examples 1 and 2 prepared with conventional dispersants. After patterning, the compound (D-1) is post-baked at 230°C, whereby the t-butoxycarbonyl group is decomposed and gasified, and the compound (D-1) can be returned to the lactam represented by the formula (2) with high absorbance before the thermally detachable group is introduced. For this reason, a cured film with sufficient light-shielding properties was obtained. The same can be said for the compounds (D-2) and (D-3).

[0179] Therefore, when a photosensitive composition using component (D) is exposed to radiation such as i-rays or h-rays while component (D) is protected by a leaving group, the transmittance of the radiation is high, and the coating film formed is sufficiently irradiated with light (for example, when radiation is irradiated from the side opposite the substrate of a substrate with a coating film, light is sufficiently irradiated up to the coating film on the substrate side), narrow lines can be formed, and pattern residue can be suppressed. Then, by post-baking at a temperature equal to or higher than the temperature at which the leaving group is eliminated after irradiation with radiation and development, the leaving group is eliminated, and a black cured product with the desired excellent light-shielding properties can be formed.

[0180] Leuco dyes such as ODB-2 are known as materials capable of improving the shielding properties after exposure. However, although the leuco dyes had small OD values ​​and high radiation transmittance before exposure, the OD values ​​were also small after exposure, and even when the leuco dye was used at a concentration of 30 mass%, the OD value increased to about 0.1 to 0.2, and the leuco dyes could not form the intended black cured product with excellent light-shielding properties.

[0181] The lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)], which is the raw material for compound (D-1) and compound (D-2), was almost insoluble in N-methylpyrrolidone, cyclohexanone, diacetone alcohol, and propylene glycol monomethyl ether acetate at 25°C. On the other hand, the (D) components such as compound (D-1), compound (D-2) and compound (D-3) were dissolved at 10% by mass or more in N-methylpyrrolidone, cyclohexanone and diacetone alcohol at 25°C, respectively, and were dissolved at 1% by mass or more in propylene glycol monomethyl ether acetate at 25°C. Thus, since the (D) component has excellent solubility in a solvent, when preparing a photosensitive composition using the (D) component, a desired (uniform) photosensitive composition can be obtained without using a so-called "dispersant". When a cured product such as a black matrix or black bank is formed from the photosensitive composition, depending on the application such as an image display device in which the cured product is used, it may be required to suppress the adverse effects of other components such as outgassing, but by using the (D) component having excellent solubility in a solvent, a desired (uniform) photosensitive composition can be obtained without using a dispersant, and by not using a dispersant, the adverse effects of other components such as outgassing can be suppressed.

[0182] The above Synthesis Examples 1 and 2 can also be said to be synthesis examples in which a component (D), which can be called a "dye," is synthesized by bonding a leaving group to a lactam pigment, which is so-called a "pigment." Before the desired cured product was formed (before post-baking), the use of component (D), which is a "dye," resulted in a photosensitive composition with excellent developability, with less foreign matter and less residue upon development, compared to Comparative Examples 1 and 2, which used pigments.

[0183] Furthermore, when the component (D) is post-baked as described above to eliminate the leaving groups, the component (D) returns to a so-called "pigment," and therefore when the desired cured product is formed (after post-baking), the cured product contains the "pigment" derived from the component (D). If the cured product contains a so-called "dye," the dye may bleed out of the cured product (e.g., black matrix, black bank) and migrate to other components of the device, such as an image display device, in which the cured product is used, such as a light-emitting layer, causing so-called "dye migration," which may adversely affect the other components. On the other hand, by post-baking component (D) as described above, the component contained in the obtained cured product can be a "pigment" rather than a "dye," and the dye migration can be suppressed.

Claims

1. A photosensitive composition comprising an alkali-soluble polymer (A), a polymerizable compound (B), a photopolymerization initiator (C), and a compound (D) represented by the following formula (1): 【Chemistry 1】 [In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a leaving group; R 1 and R 2 at least one of is a leaving group, R 3 and R 4 each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2 are each independently an integer of 0 to 4.

2. 2. The photosensitive composition according to claim 1, wherein the leaving group is a methoxymethyl group or a tert-butoxycarbonyl group.

3. 10. The photosensitive composition of claim 1 further comprising a black pigment or carbon black.

4. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 3.

5. A black matrix or black bank comprising the cured product according to claim 4.

6. A color filter comprising the black matrix according to claim 5 .

7. An image display panel comprising the color filter according to claim 6 .

8. An image display device comprising the image display panel according to claim 7.

9. An image display device comprising the black bank according to claim 5.

10. A step of applying the photosensitive composition according to any one of claims 1 to 3 onto a substrate to form a coating film; site-selectively exposing the coating to light; developing the exposed coating; and heating the developed pattern.

11. The method according to claim 10, wherein the patterned cured product is a black matrix or a black bank.

12. A compound represented by the following formula (3): 【Chemistry 2】 [In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally detachable group which is detached at a heating temperature of 250° C. or less, R 5 and R 6 at least one of the groups is the thermally detachable group, R 3 and R 4 each independently represents a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxy group, or a sulfo group; n 1 and n 2 are each independently an integer of 0 to 4.

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