Photosensitive composition and application thereof, hardened substance and manufacturing method thereof, and compound

Abstract

The invention provides a photosensitive composition with excellent sensitivity and developing property, a photosensitive composition capable of forming a cured product with excellent light shielding property, application of the photosensitive composition, the cured product, a manufacturing method of the cured product and a compound. A photosensitive composition includes an alkali-soluble polymer (A), a polymerizable compound (B), a photopolymerization initiator (C), and a compound (D) represented by formula (1) (in formula (1), R1 and R2 each independently represent a hydrogen atom or a releasable group, at least one of R1 and R2 is a releasable group, R3 and R4 each independently represent a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group, or a sulfo group, and R4 each independently represent a hydrogen atom, a fluorine atom, an organic group, a nitro group, a carboxyl group, or a sulfo group. And each of n1 and n2 independently represents an integer of 0-4). # imgabs0 #

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 the cured product, and a compound. Background Art

[0002] In a display device, a patterned light-shielding member such as a black matrix or a black bank is generally formed. As a material 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, there is known a negative photosensitive composition containing a black agent such as a benzofuranone-based black pigment, a perylene-based black pigment, or an azo-based black pigment, which has high sensitivity and can form a pattern of a desired shape (for example, Patent Document 1), and a photosensitive resin composition containing a lactam-based pigment that can achieve both pattern forming properties and suppression of the generation of residues after development (for example, Patent Document 2).

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] International Publication No. 2018 / 181311

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2021-64467 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] However, the black pigments used in the conventional photosensitive compositions described in Patent Documents 1 and 2 generally have low solubility or dispersibility in the solvent contained in the photosensitive composition, and are generally used together with a dispersant. In addition, there are problems such as insufficient developability and sometimes generation of residues (foreign matter) in places removed by development after development.

[0010] On the other hand, with the expansion of the use of display devices in recent years, the display elements are required to be of higher quality. Based on this requirement, the black matrix or black bank included in the display element is required to have higher quality (for example, higher resolution, higher light shielding property). For this purpose, a photosensitive composition having excellent sensitivity and developability and a photosensitive composition capable of forming a cured product having excellent light shielding property is required. However, if the light shielding property is improved, the transmittance of radiation (especially g-ray, h-ray and i-ray) during exposure is poor, thus falling into the paradox of reducing the sensitivity to radiation during exposure.

[0011] The present invention has been made in view of the above circumstances, and one object of the present invention is to provide a photosensitive composition having excellent sensitivity and developability and capable of forming a cured product having excellent light-shielding properties.

[0012] [Technical means to solve the problem]

[0013] The present inventors have found that the above-mentioned problems can be solved by the following structural examples. That is, the present invention provides the following photosensitive composition, cured product, black matrix, black bank, color filter, image display panel, image display device, method for producing a cured product, and compound.

[0014] The following shows a configuration example of the present disclosure.

[0015] [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).

[0016] [Chemistry 1]

[0017]

[0018] [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 them is a dissociative group,

[0019] R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group,

[0020] n 1 and n 2 are independently an integer from 0 to 4]

[0021] [2] The photosensitive composition according to [1], wherein the leaving group is a methoxymethyl group or a tert-butoxycarbonyl group.

[0022] [3] The photosensitive composition according to [1] or [2], further comprising a black pigment or carbon black.

[0023] [4] A cured product obtained by curing the photosensitive composition according to any one of [1] to [3].

[0024] [5] A black matrix or a black bank, comprising the hardened material according to [4].

[0025] [6] A color filter comprising the black matrix according to [5].

[0026] [7] An image display panel comprising the color filter according to [6].

[0027] [8] An image display device comprising the image display panel according to [7].

[0028] [9] An image display device comprising the black bank according to [5].

[0029]

[10] A method for producing a cured product, which is a method for producing a patterned cured product, comprising: applying the photosensitive composition according to any one of [1] to [3] above on a substrate to form a coating film;

[0030] A step of performing position selective exposure on the coating film;

[0031] A step of developing the exposed coating film; and

[0032] A step of heating the developed pattern.

[0033]

[11] The manufacturing method according to

[10] , wherein the patterned hardened material is a black matrix or a black bank.

[0034]

[12] A compound represented by the following formula (3).

[0035] [Chemistry 2]

[0036]

[0037] In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally desorbable group that desorbs at a heating temperature of 250° C. or less, and R 5 and R 6 At least one of them is the thermally detachable group,

[0038] R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group,

[0039] n 1 and n 2 are independently an integer from 0 to 4]

[0040] [Effects of the Invention]

[0041] According to the present invention, a photosensitive composition having excellent sensitivity and developability (particularly alkali solubility) and capable of forming a cured product having excellent light-shielding properties can be provided.

[0042] By using the photosensitive composition of one embodiment of the present invention, a cured product having a desired shape (eg, high definition) and excellent light shielding properties can be formed with little residue (foreign matter) at a location to be removed by development, high reliability, excellent adhesion to a substrate, and excellent light shielding properties.

[0043] Moreover, the photosensitive composition of one embodiment of the present invention exhibits the above-mentioned effects even when a dispersant is not used. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The UV-visible absorbance spectrum of the pattern obtained from the photosensitive composition obtained in Example 1 and the UV-visible absorbance spectrum after heating the pattern at 230°C are shown. DETAILED DESCRIPTION

[0045] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0046] In addition, in this specification, "(meth)acrylic acid" means including "acrylic acid" and "methacrylic acid". "(meth)acryloyl" means including "acryloyl" and "methacryloyl".

[0047] The term "alkali-soluble" means that the compound is soluble in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 25°C.

[0048] Furthermore, the 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 % tetramethylammonium hydroxide aqueous solution at 25° C. Whether the polymer is alkali-soluble can be determined by the presence or absence of a precipitate.

[0049] 《Photosensitive composition》

[0050] The photosensitive composition of the present disclosure (hereinafter also referred to as "the present 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)"). In addition, unless otherwise specified, each component may be used alone or in combination of two or more.

[0051] The present composition is a composition having excellent sensitivity and developability (particularly alkali solubility), and can form a cured product having excellent light-shielding properties.

[0052] Conventionally, when forming a black light-shielding pattern, a black resist prepared by dispersing carbon black, perylene pigment, lactam pigment, etc. in a solvent using a dispersant is exposed, developed, calcined, etc. However, if the light-shielding property is improved, radiation, etc. cannot pass through during exposure, so there is a problem of reduced sensitivity or resolution of the resist.

[0053] As described above, conventionally, a dispersant is used to disperse a pigment in a solvent, but uniform dispersion is difficult, and there is a problem that poorly dispersed portions remain as residues during development.

[0054] In one embodiment of the present invention, it is preferred to introduce a heat-detachable group having excellent solvent solubility into the lactam pigment, thereby solving these problems. Thus, the lactam pigment can be dissolved in the solvent at the molecular level, and the generation of residue during development can be greatly suppressed.

[0055] In addition, by introducing (thermal) leaving groups, such as Figure 1 As shown, the transmittance of radiation can be increased, thereby improving the sensitivity. Furthermore, by calcining (post-baking) at a temperature at which the thermally detachable group is detached, the thermally detachable group contained in the (D) component is decomposed and gasified, and the (D) component can be restored from the dye to the original lactam pigment. Therefore, by the calcination, the light-shielding property originally possessed by the lactam pigment can be exerted. In addition, it has the following advantages: the solubility relative to the solvent is lost due to the decomposition of the thermally detachable group, and the "migration" described later, which becomes a problem in the dye, is not likely to occur. Furthermore, the present composition does not use a dispersant, or even if a dispersant is used, it can be used in a smaller amount than before, so it also has the advantage of suppressing the generation of smoke or decomposition products derived from the dispersant during calcination.

[0056] Furthermore, since the component (D) has excellent solubility in a solvent, the present composition can obtain a desired (uniform) photosensitive composition even without using a dispersant, thereby achieving the above-mentioned effect.

[0057] When a cured product such as a black matrix or a black bank is formed from the present composition, it may be required to suppress gas evolution, etc., depending on the application of the image display device using the cured product. However, by using the component (D) having excellent solubility in a solvent, a desired (uniform) photosensitive composition can be obtained even without using a dispersant, and since no dispersant is used, problems such as gas evolution originating from the dispersant can be suppressed.

[0058] Furthermore, the component (D) can be called a so-called "dye" having excellent solubility in a solvent, but after the detachable group is released by post-baking the component (D) as described above, the solubility of the component (D) in a solvent decreases and the component becomes a so-called "pigment". Therefore, for example, when a cured product is formed by post-baking, the cured product contains a "pigment" derived from the component (D).

[0059] If a so-called "dye" is contained in the cured product, the dye may ooze out of the cured product (for example, a black matrix, a black bank) and move to other components such as a light-emitting layer of an image display device or the like using the cured product, so-called "dye migration" may occur, resulting in black spots on other components. On the other hand, by post-baking the component (D) as described above, the component contained in the obtained cured product can be made into a "pigment" instead of a "dye", thereby suppressing the above-mentioned dye migration.

[0060] [Component (A): alkali-soluble polymer (A)]

[0061] The component (A) is not particularly limited as long as it is an alkali-soluble polymer, and is preferably a polymer having an acidic group such as a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, or a fluorinated hydroxyalkyl group (a hydroxyalkyl group in which a part of hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms).

[0062] Examples of polymers having an acidic group include polymers having phenolic hydroxyl groups such as novolac resins, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, phenol-dicyclopentadiene condensation resins, polybenzoxazole precursors, polyhydroxystyrene, and copolymers obtained using hydroxystyrene and styrene; and polymers having carboxyl groups such as carboxyl-containing epoxy (meth)acrylate resins and polyamic acids whose main chains contain a novolac-type skeleton.

[0063] Examples of polymers having an acidic group include copolymers 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)"). A (meth)acrylic acid polymer having an acidic group is particularly preferred.

[0064] The unsaturated monomer (a1) and the unsaturated monomer (a2) can be used alone or in combination of two or more.

[0065] Examples of the unsaturated monomer (a1) include: unsaturated monomers containing a carboxyl group, such as (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxy polycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid; unsaturated monomers containing a phenolic hydroxyl group, such as hydroxystyrene, p-isopropenylphenol, hydroxyphenyl(meth)acrylate, and hydroxyphenyl(meth)acrylamide; and unsaturated monomers containing a fluorinated hydroxyalkyl group, such as 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl)styrene.

[0066] As unsaturated monomers (a2), for example, there can be listed: N-substituted maleimides such as N-arylmaleimide, N-alkylmaleimide, and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and its derivatives; (meth)acrylates such as alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic (meth)acrylates, (meth)acrylates having cyclic ether rings such as oxirane rings, oxetane rings, and oxolane rings; aromatic ring-containing silane compounds such as styrene-containing silane compounds; vinyl ethers such as alicyclic vinyl ethers; macromolecular monomers having a mono(meth)acryloyl group at the end of a polymer chain such as an aromatic vinyl compound polymer chain, a (meth)acrylate polymer chain, and a polysiloxane molecular chain.

[0067] More specifically, examples of the unsaturated monomer (a1) and the unsaturated monomer (a2) include monomers described in JP-A-2015-004968, JP-A-2008-233346, and JP-A-2009-229567.

[0068] Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 11-258416, Japanese Patent Laid-Open No. 11-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 11-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-31308, Japanese Patent Laid-Open No. 10 ... Copolymers disclosed in Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728, Japanese Patent Laid-Open No. 2006-201549, Japanese Patent Laid-Open No. 2007-128062, Japanese Patent Laid-Open No. 2008-233563, Japanese Patent Laid-Open No. 2017-181928, Japanese Patent Laid-Open No. 2017-173376, etc.

[0069] 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% by mass, more preferably 10% to 40% by mass. By using the unsaturated monomer (a1) within this range, a composition having excellent alkali developability and storage stability can be easily obtained.

[0070] The copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) can be produced by a conventional method, and its structure, weight average molecular weight, and molecular weight distribution can be controlled by the methods disclosed in, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, and International Publication No. 2007 / 029871.

[0071] In addition, as the component (A), a carboxyl-containing polymer having a polymerizable unsaturated bond (e.g., a carbon-carbon double bond in a (meth)acryloyl group) in a side chain may be used, for example, as disclosed in Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc.

[0072] Furthermore, as the component (A), alkali-soluble polysiloxane, alkali-soluble cardoresin, alkali-soluble polyimide, polybenzoxazole, etc. can also be mentioned.

[0073] Specific examples of alkali-soluble polysiloxanes include copolymers disclosed in International Publication No. 2017 / 188047, International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, Japanese Patent Application Publication No. 2020-184010, Japanese Patent Application Publication No. 2013-114238, Japanese Patent Application Publication No. 2012-53381, Japanese Patent Application Publication No. 2010-32977, etc.

[0074] As the alkali-soluble polysiloxane, silsesquioxane having a first structural unit represented by the following formula (4) and a second structural unit represented by the following formula (5) is preferred.

[0075] [Chemistry 3]

[0076]

[0077] (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 carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof)

[0078] In formula (4), X is preferably a group represented by the following formula (6).

[0079] In formula (5), Y is preferably a group represented by the following formula (7a) or formula (7b).

[0080] [Chemistry 4]

[0081]

[0082] In formula (6), formula (7a) and formula (7b), R 7 are independently a hydrogen atom or a methyl group; R 8 are each independently an alkanediyl group having 2 to 10 carbon atoms; 9 is a divalent organic group; R 10 is a single bond or a divalent organic group; Z is each independently a sulfur atom; * indicates a bonding site.

[0083] The alkali-soluble cardol resin is not particularly limited as long as it is soluble in an alkali developer, and is preferably a resin containing one or more anionic groups such as a carboxyl group, a sulfonic acid group, and a phosphonic acid group.

[0084] The cardo resin refers to a resin having a cardo skeleton. The cardo skeleton refers to a skeleton in which two aromatic groups are bonded to one carbon atom constituting a cyclic structure via a single bond.

[0085] The cardol resin is preferably a radical polymerizable resin, and can be obtained, for example, by reacting an epoxy resin containing a cardol structure with at least one compound having an acidic group selected from (meth)acrylic acid, dicarboxylic anhydride, and tetracarboxylic dianhydride.

[0086] Commercially available products of free radical polymerizable cardo-based resins include, for example, "WR-301" manufactured by ADEKA Co., Ltd.; "V-259ME" manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; and "Ogsol CR-TR1", "Ogsol CR-TR2", "Ogsol CR-TR3", "Ogsol CR-TR4", "Ogsol CR-TR5" and "Ogsol CR-TR6" manufactured by Osaka Gas Chemical Co., Ltd.

[0087] From the viewpoint of alkali developability, the acid value of the alkali-soluble cardol resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less, and more preferably 20 mgKOH / g or more and 200 mgKOH / g or less.

[0088] Specific examples of alkali-soluble polyimides or polybenzoxazoles include copolymers disclosed in International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, International Publication No. 2017 / 057281, International Publication No. 2017 / 159476, International Publication No. 2017 / 073481, International Publication No. 2017 / 038828, International Publication No. 2016 / 148176, Japanese Patent Application Publication No. 2015-114355, Japanese Patent Application Publication No. 2013-164432, Japanese Patent Application Publication No. 2010-72143, etc.

[0089] The weight average molecular weight (Mw) of the component (A) as measured by gel permeation chromatography (GPC) is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000.

[0090] The ratio (Mw / Mn) of the Mw of the component (A) to the number average molecular weight (Mn) is preferably 1.0 to 10.0, more preferably 1.0 to 5.0, and still more preferably 1.0 to 3.0.

[0091] In addition, Mw and Mn are specifically polystyrene-equivalent values ​​measured by the method described in the following Examples.

[0092] The content of component (A) in the present composition is preferably 10% by mass or more, more preferably 15% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, relative to 100% by mass of the solid content of the present composition (i.e., components other than the solvent in the present composition).

[0093] When the content of the component (A) is within the above range, a composition having excellent alkali developability and storage stability can be easily obtained, and a cured product having excellent light-shielding properties can be easily formed.

[0094] [Component (B): polymerizable compound (B)]

[0095] The component (B) is an essential component for forming a cured product of the present composition and is not particularly limited, but is preferably a compound having a polymerizable carbon-carbon unsaturated bond.

[0096] The component (B) may be any polymerizable compound other than the component (A), 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.

[0097] (B) Component may be any of a monofunctional compound and a polyfunctional compound. In addition, as (B) component, a monofunctional compound and a polyfunctional compound may be used in combination.

[0098] Specific examples of the component (B) when it is a monofunctional compound include: (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Among these, a compound containing a (meth)acryloyl group is preferred, and a compound containing a (meth)acryloyl group that is at least one selected from the group consisting of (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure is more preferred.

[0099] Specific examples of the compound include (meth)acrylates having a chain structure, such as alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and polyoxyalkylene (meth)acrylates.

[0100] Examples of the alkyl (meth)acrylate 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.

[0101] Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0102] As an alkoxyalkyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, etc. are mentioned.

[0103] Examples of the polyoxyalkylene (meth)acrylate 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.

[0104] Examples of the (meth)acrylate having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate, tricyclo[5.2.1.02,5]decane-8-yloxyethyl (meth)acrylate, and isobornyl (meth)acrylate.

[0105] Examples of the (meth)acrylate having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, naphthyl methyl (meth)acrylate, naphthyl ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenyl methyl (meth)acrylate, p-phenoxyphenyl methyl (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.

[0106] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl) (meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0107] Examples of the chain vinyl compound include propylene, butene, pentene, and hexene.

[0108] Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, tert-butoxystyrene, and vinylnaphthalene.

[0109] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0110] Specific examples of the component (B) when it is a polyfunctional compound include polyfunctional (meth)acrylates, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds.

[0111] Examples of the multifunctional (meth)acrylate include difunctional (meth)acrylates, trifunctional or higher (meth)acrylates, etc. Specific examples of these difunctional (meth)acrylates include 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, ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, ethoxylated cresol novolac di(meth)acrylate, and ethoxylated biphenyl di(meth)acrylate.

[0112] Examples of trifunctional or higher-functional (meth)acrylates 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), tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, -(meth)acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, isocyanuric acid tri(2-(meth)acryloyloxyethyl) ester, carboxyl-containing polyacid-modified (meth)acrylic acid oligomer, a compound having a linear alkylene and alicyclic structure and having two or more isocyanate groups, and a polyfunctional urethane acrylate compound obtained by using a compound having one or more hydroxyl groups and three, four or five (meth)acryloyloxy groups in the molecule.

[0113] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0114] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0115] The content of the component (B) in the present composition is preferably 3% by mass or more, more preferably 5% by mass or more, and is 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.

[0116] When the content of the component (B) is within the above range, a photosensitive composition that exhibits good sensitivity, resolution, and solvent resistance can be easily obtained.

[0117] [Component (C): photopolymerization initiator (C)]

[0118] The component (C) is not particularly limited, but is preferably a photoradical polymerization initiator that generates radicals in response to radiation and initiates polymerization. Examples of the component (C) include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0119] Examples of the O-acyl oxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-octane-1-one oxime-O-acetate, and 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-1-(O-acetyl oxime). 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime) , ethyl ketone-1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl〕-1-(O-acetyl oxime), ethyl ketone-1-〔9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl〕-1-(O-acetyl oxime), ethyl ketone-1-〔9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1, [3-dioxolyl)methoxybenzoyl}-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1,2-propanedione-3-cyclohexyl-1-〔4-(phenylthio)phenyl〕-1-(O-acetyl oxime), O-acyl oxime compounds containing a fluorene skeleton represented by the following formula (C-1) and formula (C-2), and O-acyl oxime compounds containing a diphenyl sulfide skeleton represented by the following formula (C-3).

[0120] [Chemistry 5]

[0121]

[0122] Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.

[0123] Specific examples of the α-amino ketone compound 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.

[0124] Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone.

[0125] 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.

[0126] As an acylphosphine oxide compound, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are mentioned, for example.

[0127] As the component (C), an O-acyl oxime compound is preferred. From the viewpoint of being able to provide a better contrast of the cured film, an O-acyl oxime compound having a diphenyl sulfide skeleton, an O-acyl oxime compound having a carbazole skeleton, or an O-acyl oxime compound having a fluorene skeleton is more preferred. An O-acyl oxime compound having a diphenyl sulfide skeleton or an O-acyl oxime compound having a fluorene skeleton is more preferred.

[0128] As the component (C), the 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.

[0129] 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% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more relative to the total amount of the component (C) used, in order to further improve the heat resistance and solvent resistance of the obtained cured film.

[0130] The content of the component (C) in the present composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, based on 100% by mass of the solid content of the present composition.

[0131] When the content of the component (C) is within the above range, a photosensitive composition that exhibits good sensitivity, resolution, and solvent resistance can be easily obtained.

[0132] [Component (D): Compound (D) represented by formula (1)]

[0133] The 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. The component (D) has excellent solubility in solvents at room temperature, and is therefore also classified as a "dye" among colorants.

[0134] [Chemistry 6]

[0135]

[0136] [In formula (1), R 1 and R 2 are independently a hydrogen atom or a leaving group, R 1 and R 2 At least one of them is a dissociative group,

[0137] R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group,

[0138] n 1 and n 2 are independently an integer from 0 to 4]

[0139] In this specification, the term "leaving group" refers to a group that is detached by heat, light, etc. and replaced by a hydrogen atom. That is, component (D) is a component that is detached by heat, light, etc. to form a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)").

[0140] The detachable group in the component (D) is preferably a group that is detached by heat and replaced by a hydrogen atom (hereinafter also referred to as a "thermal detachable group"), more preferably a thermal detachable group that detaches at a heating temperature of 250°C or lower, further preferably a thermal detachable group that detaches at a heating temperature of 230°C or lower, and particularly preferably a thermal detachable group that detaches at a heating temperature of 200°C or lower.

[0141] Examples of the leaving group include a methoxymethyl group (MOM (methoxymethyl) group), an alkyloxycarbonyl group having a straight chain or branched alkyl group having 1 to 10 carbon atoms, an alkenyloxycarbonyl group having a straight chain or branched alkenyl group having 1 to 10 carbon atoms, and an oxycarbonyl group having a cyclic structure having 1 to 20 carbon atoms. A part of these groups may be substituted by at least one selected from a silicon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a halogen atom, and the alkyl group or the alkenyl group may have an alkoxy group having 1 to 3 carbon atoms. More specifically, examples thereof 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).

[0142] Among these, methoxymethyl and tert-butoxycarbonyl are preferred because a compound (1) having excellent solubility in a solvent and a dissociable group can be obtained by heating at a low temperature (eg, 200° C.).

[0143] In the above formula (1), R 1 and R 2 The above-mentioned leaving groups are preferred, and thermal leaving groups are more preferred.

[0144] In the formula (1), R 3 and R 4 Preferably they are each independently a chlorine atom or an organic group.

[0145] 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.

[0146] In the formula (1), n 1 and n 2 Each of them is independently preferably 0 to 2, and more preferably 0. 1 or 2 When it is an integer of 1 or more, that is, when there is a substituent at the 4-7 position of the indolinone ring in compound (1), it is preferred to have a substituent at the 4- or 6-position in view of ease of production and availability.

[0147] Compound (1) has EE isomer, ZZ isomer, and EZ isomer as geometric isomers, and may be a single compound of any of these or a mixture of these geometric isomers.

[0148] 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 indolinone ring of Compound (2) by a conventional amine protection method or alcohol protection method. Compound (2) can also be a commercially available product.

[0149] Alternatively, compound (1) can be obtained by reacting isatin with a compound used as a raw material of the leaving group such as dialkyl dicarbonate, dienyl dicarbonate, dialkoxyalkyl dicarbonate, alkyl chlorocarboxylic acid, alkenyl chlorocarboxylic acid, or 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-carbonyloxyalkyl isatin, and then preparing the compound according to Japanese Patent Laid-Open No. 2016-84425, Japanese Patent Laid-Open No. 2015-121753, International Publication No. 2014 / 071524, and Journal of the American Chemical Society. Society, J.Am.Chem.Soc.) (2013, 135, 12168.), "Journal of the American Chemical Society (J.Am.Chem.Soc.)" (2015, 137, 15947.), etc., 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 catalyst or a base catalyst.

[0150] Examples of acid catalysts include organic carboxylic acids such as hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, and benzoic acid. Examples of base catalysts include organic amines such as n-butyl lithium, lithium diisopropylamide, and triethylamine, organic bases such as pyridines, and inorganic bases such as sodium hydride, sodium hydroxide, and potassium carbonate.

[0151] The isatin can be synthesized, for example, by condensing chloral hydrate, aniline and hydroxylamine in sulfuric acid. Alternatively, aniline having an organic group such as an alkyl group or an alkoxy group may be used instead of unsubstituted aniline to form R of the compound (1). 3 and / or R 4 The cohesion and solubility can be adjusted by introducing an organic group therein. In addition, the cohesion and solubility can be adjusted by mixing a compound (1) having a structure other than the target compound or a plurality of compounds (1) having different structures.

[0152] [Chemistry 5]

[0153]

[0154] [In formula (2), R 3 , R 4 、n 1 and n 2 The same symbols as in the formula (1) have the same meanings as those in the formula (1)]

[0155] Compound (2) is a compound generally known as a lactam pigment and can be used as a black pigment. A cured film containing compound (2) has excellent light-shielding properties. Therefore, a cured product containing compound (2) produced by releasing a leaving group from compound (1) has excellent light-shielding properties.

[0156] In addition, compound (2) has poor solubility in solvents at room temperature and is therefore also classified as a "pigment" among colorants. A cured product containing compound (2) as a colorant has low solubility, and therefore dissolution (migration) into a light-emitting layer or the like when the cured product is used can be suppressed.

[0157] The content of the component (D) in the present composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more, relative to 100% by mass of the solid content of the present composition, and is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 30% by mass or less.

[0158] When the content of the component (D) is within the above range, the radiation (particularly g-ray, h-ray and i-ray) transmittance is excellent, so a photosensitive composition with excellent sensitivity can be easily obtained, and a cured product with excellent light-shielding properties can be easily formed.

[0159] [Other ingredients]

[0160] The present composition may contain, in addition to the above-mentioned components (A) to (D), further components other than these (hereinafter also referred to as "other components") within a range not impairing the effects of the present invention.

[0161] Examples of the 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.

[0162] The blending ratio of these other components is appropriately selected according to each component within a range that does not impair the effects of the present invention.

[0163] Solvent

[0164] The present composition is preferably a liquid composition obtained by dissolving or dispersing the components (A) to (D) and other components prepared as necessary in a solvent (hereinafter also referred to as “solvent (E)”).

[0165] The solvent (E) is preferably an organic solvent that dissolves the components formulated in the present composition and does not react with the components.

[0166] 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, 3-methoxypropionic acid methyl ester, and 3-ethoxypropionic acid ethyl ester; 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; keto alcohols such as diacetone alcohol; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0167] Since the present composition contains the component (D), the solvent (E) is preferably a mixed solvent containing the following first solvent and second solvent.

[0168] The first solvent is 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, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 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.

[0169] The second solvent is 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 ketone alcohols such as diacetone alcohol.

[0170] The compound (1) as the component (D) tends to have particularly high solubility in the second solvent. More specifically, the solubility of the compound (1) in the second solvent at 25°C is usually 10% by mass or more.

[0171] When a mixed solvent of the first solvent and the second solvent is used as the solvent (E), in terms of fully ensuring the solubility of the component (D) in the solvent, the content of the second solvent is preferably set to 30% by mass or more, more preferably to 40% by mass or more relative to the total solvent amount in the present composition. In addition, in terms of the solubility or coating properties of each component, the content of the second solvent is preferably set to 95% by mass or less, more preferably to 90% by mass or less.

[0172] When a solvent (E) is formulated in the present composition, it is preferred to use the solvent (E) so that the solid content concentration of the present composition is within the following range in terms of solubility / dispersibility of components (A) to (D) or coating properties when the present composition is applied to a substrate.

[0173] ・Coloring agents other than component (D)

[0174] In the present composition, only the component (D) may be used as the colorant. However, by using a colorant other than the component (D), the light shielding property of a cured product obtained from the present composition tends to be improved.

[0175] Examples of the colorant 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 the component (D).

[0176] 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.

[0177] When a colorant other than the component (D) is blended in the present composition, a composition having excellent sensitivity, developability, and radiation (particularly g-ray, h-ray, and i-ray) transmittance can be easily obtained, thereby easily forming a cured product having excellent light-shielding properties. In this case, the amount of the colorant other than the component (D) blended is preferably 0.1% by mass or more, more preferably 1% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, based on 100% by mass of the solid content of the present composition.

[0178] In addition, from the viewpoint that a composition having excellent sensitivity, developability, and radiation transmittance (particularly g-rays, h-rays, and i-rays) can be easily obtained, the amount of colorant other than component (D) contained in the present composition is preferably as small as possible, and therefore, it is also preferred that no colorant other than component (D) is contained.

[0179] When using a pigment as a colorant other than component (D), the method of using the pigment is not particularly limited, and the pigment can be used as a powder or as a dispersion. Among these, in terms of solvent solubility or solvent dispersibility, the pigment is preferably masterbatched and used in the preparation of the present composition as a pigment masterbatch dispersion.

[0180] It is preferred to use a resin in the pigment masterbatch. The resin is not particularly limited, but is preferably the same resin as the component (A). In order to improve dispersibility, it is preferred to mix a dispersant described below in the pigment masterbatch.

[0181] As the dispersion medium in the pigment masterbatch dispersion, for example, 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 can be used.

[0182] Dispersants

[0183] When a pigment is used as a colorant other than component (D), it is preferred to finely disperse the pigment and stabilize its dispersion state in terms of the quality stability of the composition, so it is preferred to use a dispersant. In addition, a dispersant may be used together with a dispersant. In addition, when no pigment is used, when the solubility of component (D) is poor, a dispersant may be used for the purpose of maintaining a stable dispersion state.

[0184] 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 functional groups such as a carboxyl group; a phosphoric acid group; a sulfonic acid group; a base thereof; a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is preferred. Among these, a polymer dispersant having a basic functional group such as a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is particularly preferred because a small amount of the dispersant can be used to disperse the pigment.

[0185] In addition, examples of polymer dispersants include: carbamate dispersants, acrylic acid dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants obtained using monomers and macromonomers having an amino group, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0186] When a pigment and a dispersant are mixed in the present composition, the amount of the dispersant mixed is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and further preferably 20 to 60 parts by mass, relative to 100 parts by mass of the pigment. In addition, when a dispersant is mixed without using a pigment in the present composition, the amount of the dispersant mixed is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, and further preferably 20 to 60 parts by mass, relative to 100 parts by mass of the component (D).

[0187] In view of the ease of production and production cost of the present composition, it is preferred that other components that may be contained in the present composition be as small as possible. Also, since gas derived from the dispersant may be generated from the cured film, it is also preferred that no dispersant be contained.

[0188] Dispersing aids

[0189] When a dispersant is used in the present composition, a dispersing aid may be used together with the dispersant.

[0190] Examples of the dispersing aid include pigment derivatives.

[0191] Examples of the pigments in the pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolopyrrole pigments.

[0192] Examples of the pigment derivative include compounds having a sulfonic acid group, sulfonamide group, quaternary salt of sulfonamide group, phthalimidomethyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group or the like bonded to the pigment skeleton directly or via an alkyl group, aryl group or heterocyclic group.

[0193] Surfactants

[0194] For example, the coating properties of the present composition can be improved by using a surfactant in the present composition.

[0195] Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0196] As the fluorine-based surfactant, a commercially available product can be used, and examples of the commercially available product include: Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-251, Megafac F-430, Megafac F-554, Megafac F-563 (manufactured by DIC Corporation); Fluorad FC430, Fluorad FC431, Fluorad FC432, Fluorad FC433, Fluorad FC434, Fluorad FC435, Fluorad FC436, Fluorad FC437, Fluorad FC438, Fluorad FC439, Fluorad FC440, Fluorad FC441, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad FC449, Fluorad FC448, Fluorad FC449, Fluorad FC441, Fluorad FC443 ...2, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad )FC431 (manufactured by Sumitomo 3M Co., Ltd.); AsahiGuard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (AGC Seimei Chemical Co., Ltd. (manufactured by SEIMI Chemical); Polyflow No.75, Polyflow No.95 (manufactured by Kyoeisha Chemical); FTX-218 (manufactured by NEOS); Eftop EF301, Eftop EF303, Eftop EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), etc.

[0197] As the silicone surfactant, commercially available products can 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, PAINTAD 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (Dow Toray) BYK-340 (manufactured by BYK-Chemie Japan Co., Ltd.), etc.

[0198] Examples of the nonionic surfactant 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.

[0199] When a surfactant is formulated in the present composition, the amount of the surfactant formulated is preferably 0.01% to 1.5% by mass, more preferably 0.02% to 1.2% by mass, and even more preferably 0.05% to 1.0% by mass, relative to 100% by mass of the solid content of the present composition.

[0200] Antioxidants

[0201] For example, by using an antioxidant, decomposition and degradation of polymer molecules in the present composition can be suppressed, and durability can be improved.

[0202] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0203] When an antioxidant is formulated in the present composition, the amount of the antioxidant formulated is preferably 0.01 to 1.5% by mass, more preferably 0.02 to 1.2% by mass, and even more preferably 0.05 to 1.0% by mass, relative to 100% by mass of the solid content of the present composition.

[0204] ·Adhesives

[0205] By using the present composition containing the adhesion aid, the adhesion between the formed cured product and the substrate (adhered body) can be improved, and the peeling of the cured product from the substrate in the development step or the like can be suppressed.

[0206] Examples of the adhesion aid include functional silane coupling agents having a reactive functional group.

[0207] Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0208] Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0209] When a close contact aid is blended in the present composition, the blending amount of the close contact aid is preferably 0.01 to 4.0% by mass, more preferably 0.1 to 4.0% by mass, based on 100% by mass of the solid content of the present composition.

[0210] [Method for preparing the present composition]

[0211] The present composition can be prepared, for example, by uniformly stirring and mixing the components (A) to (D) and any other components, and uniformly dissolving or dispersing them. The mixing can be performed using a conventional agitator such as a roll mill, a ball mill, or a sand mill.

[0212] After the components are mixed, the obtained mixture may be filtered using a filter having a pore size of 2 μm or less, for example, as necessary.

[0213] The solid content concentration of this composition (that is, the total mass of the components other than the solvent in this composition relative to the total mass of this composition) can be appropriately selected considering viscosity or volatility. The solid content concentration of this composition is preferably 1% by mass to 60% by mass, more preferably 2% by mass to 50% by mass, and then preferably 5% by mass to 40% by mass. If the solid content concentration is more than the lower limit, the film thickness of the coating can be fully ensured when this composition is applied to the substrate (adhered body), and it is preferred in terms of these aspects. In addition, if the solid content concentration is below the upper limit, the viscosity of this composition can be appropriately improved, and good coating properties can be ensured, and it is preferred in terms of these aspects.

[0214] The present composition can be suitably used to form a cured product having light-shielding properties such as a black matrix or a black bank used in a color filter, etc. The cured product obtained from the present composition, especially a black matrix or a black bank having excellent light-shielding properties, can be particularly effectively used in liquid crystal display elements, solid-state imaging elements, color sensors, organic electroluminescence (EL) display elements, electronic paper, etc.

[0215] Hardened

[0216] 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 is specifically formed by irradiating the present composition with radiation.

[0217] The present cured product can be formed into a cured product of a desired shape by, for example, controlling the shape of a coating film when the present composition is applied or by combining site selective exposure and development.

[0218] The present cured product can be particularly preferably used as a black matrix or a black bank in a color filter or the like used in various image display devices.

[0219] In addition, the black component that separates each unit cell of red, green, blue (Red-Green-Blue, RGB) in the color filter is called a black matrix. In addition, a partition wall is formed on the substrate in advance, and an organic EL light-emitting layer is formed in the concave space divided by the partition wall by an inkjet method, etc. The partition wall that is blackened to prevent light leakage between pixels is called a black bank.

[0220] The color filter including the black matrix formed by the hardened material formed by using the present composition can be suitably used in an image display panel. The image display panel can be suitably used in various image display devices such as a liquid crystal display device or an organic EL display device. In addition, it can also be suitably used in a touch panel having both an image display panel and a surface sensor including an electrostatic capacitance electrode or a resistance electrode.

[0221] [Method for producing the present hardened product]

[0222] The method for producing the present cured product comprises the step of irradiating the present composition with radiation. When irradiating the radiation, position selective irradiation may be performed using a mask having a predetermined pattern, or development may be performed after irradiation. Furthermore, heat treatment may be performed after irradiation.

[0223] The present composition is particularly suitable as a negative-type 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.

[0224] As preferred examples of the method for producing the present cured product, the following first production method and second production method can be mentioned.

[0225] <First Manufacturing Method>

[0226] The first production method is a method comprising the following steps (I) to (IV), and may further comprise the following step (V) as necessary.

[0227] (Step (I): coating step)

[0228] Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition on the substrate.

[0229] Examples of the substrate include a glass substrate, a silicon wafer, a plastic substrate, and substrates having a color resist, an overcoat layer, an antireflection film, various metal thin films, a sealing film, and the like formed on the surface thereof.

[0230] 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.

[0231] Various elements (for example, light-receiving elements such as photodiodes, or light-emitting elements such as organic light-emitting diodes) may be provided in advance in the substrate.

[0232] As a coating method of the present composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, an ink jet method, etc. can be used. As a coating method, spin coating method, bar coating method or slot die coating method is preferable among these.

[0233] After the composition is applied to the substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping. The prebaking conditions may be appropriately set according to the type or proportion of each component used in the composition, for example, at 60°C to 130°C for 30 seconds to 10 minutes.

[0234] In addition, the pre-baking is preferably performed at a temperature at which the leaving group in the component (D) is not left.

[0235] The film thickness of the formed coating film is preferably 0.2 μm or more, more preferably 0.3 μm to 5 μm, and still more preferably 0.4 μm to 3 μm, as the film thickness after prebaking.

[0236] (Step (II): Exposure Step)

[0237] Step (II) is a step of irradiating the coating film formed in step (I) with radiation in a site-selective manner. By the radiation irradiation, a curing reaction proceeds in the exposed portion, and a cured product is obtained in which the exposed portion is cured.

[0238] In step (II), the site-selective radiation 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 also be a multi-tone mask such as a halftone mask or a gray tone mask.

[0239] As a radiation irradiated to a coating film, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams are mentioned, for example.

[0240] 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).

[0241] Examples of X-rays include synchrotron radiation.

[0242] As a charged particle beam, an electron beam is mentioned, for example.

[0243] Among these radiations, ultraviolet rays are preferred, and ultraviolet rays including g-rays, h-rays, and i-rays are more preferred.

[0244] Examples of the light source used for radiation irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and a light emitting diode (LED) lamp.

[0245] The radiation exposure dose is preferably 100 J / m 2 ~50,000J / m 2 (10mJ / m 2 ~5,000mJ / cm 2 ), more preferably 100 J / m 2 ~6,000J / m 2 (10mJ / cm 2 ~600mJ / cm 2 ).

[0246] (Step (III): Development Step)

[0247] 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). The coating film formed on the unexposed portion on the substrate can be removed by the development step, thereby forming a patterned (e.g., a concave-convex pattern formed by a plurality of regularly arranged linear cured products) cured products remaining in the exposed portion (e.g., linear cured products) on the substrate.

[0248] As the developer, an aqueous solution of an alkali (alkaline compound) can be mentioned.

[0249] Examples of the base 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.

[0250] Alternatively, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution, or a small amount of various organic solvents capable of dissolving the present composition may be added.

[0251] The concentration of the developer can be appropriately determined depending on the composition of the composition, and is usually 0.01% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass.

[0252] As the developing method, for example, an appropriate method such as a coating method, a dipping method, a shaking dipping method, a shower method or the like can be adopted.

[0253] The development time may be appropriately adjusted according to the composition of the present composition, and is, for example, 20 seconds to 120 seconds.

[0254] After the development step, a step of washing the developed patterned substrate with pure water or the like may be performed as necessary.

[0255] In addition, a step of drying the patterned substrate after development or the cleaning may be performed. The drying conditions are not particularly limited, and for example, the same conditions as those for the pre-baking can be mentioned.

[0256] Since the present composition has excellent ultraviolet (especially g-ray, h-ray and i-ray) transmittance and excellent sensitivity during exposure, the patterned cured product obtained from the present composition is well in close contact with the substrate and can form a pattern with a fine line width.

[0257] (Step (IV): Post-baking step)

[0258] Step (IV) is a step of heating the developed pattern to release the releasable group from the component (D) in the patterned cured product. Alternatively, step (IV) may be a step of removing the solvent and water in the patterned cured product and further curing the composition by thermal crosslinking to improve adhesion to the substrate and corrosion resistance.

[0259] The heat treatment can be performed, for example, using a heating device such as an oven or a hot plate, and can be performed in any environment such as a nitrogen atmosphere or the air.

[0260] The heating temperature in step (IV) may be appropriately selected depending on the substrate or the present composition used, and is preferably a temperature higher than the temperature at which the leaving group is released from component (D). It also depends on the type of the leaving group, and is more preferably 150°C to 270°C, and even more preferably 180°C to 230°C.

[0261] The heating time can be appropriately set according to the type of heating device, etc. For example, when a hot plate is used for heating, the heating time is, for example, 5 minutes to 60 minutes. In addition, when an oven is used for heating, the heating time is, for example, 10 minutes to 90 minutes.

[0262] In step (IV), a step baking method in which the heating treatment is performed multiple times may be used.

[0263] (Step (V): Post-exposure step)

[0264] Step (V) is a step of further irradiating the hardened material obtained in step (III) after development and / or the hardened material obtained in step (IV) with radiation. Among these, the step of further irradiating the hardened material obtained in step (IV) with radiation is preferred in terms of being able to easily form a hardened material of a desired shape.

[0265] By irradiating with radiation in the step (V) (hereinafter also referred to as “post-exposure”), heat resistance, chemical resistance, etc. can be further improved, and a highly reliable cured product can be easily formed.

[0266] Among these, the type of radiation or exposure conditions in the post-exposure may be the same as those in step (II). In addition, the wavelength or irradiation amount of the irradiation light, the light source and other conditions in the post-exposure may be the same as or different from those in step (II).

[0267] <Second Manufacturing Method>

[0268] The second manufacturing method includes a step of inkjet coating the composition on a substrate to form a pattern. In the second manufacturing method, a pattern of a desired shape can be directly formed on the substrate by inkjet coating, and then the same step (IV) as the first manufacturing method is performed to form a desired hardened product.

[0269] In addition, the second manufacturing method may include the same step as the step (V) in the first manufacturing method.

[0270] 《Image display device》

[0271] The image display device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventional structure other than including the present cured product.

[0272] Examples of the image display device include a liquid crystal display (LCD), an organic EL using an organic light emitting diode (OLED), a μLED display, an electrochromic display (ECD), an electroluminescent display (ELD), and a display using a quantum dot-organic EL (QD-OLED).

[0273] Compounds

[0274] The compound disclosed in the present invention is a compound represented by the following formula (3) (hereinafter also referred to as “compound (3)”).

[0275] Such compound (3) has excellent solubility in a solvent at room temperature. By using such compound (3), the photosensitive composition has excellent sensitivity and developability, and a cured product having excellent light-shielding properties can be easily formed.

[0276] [Chemistry 8]

[0277]

[0278] In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally desorbable group that desorbs at a heating temperature of 250° C. or less, and R 5 and R 6 At least one of them is the thermally detachable group,

[0279] R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group,

[0280] n 1 and n 2 are independently an integer from 0 to 4]

[0281] In the formula, R 3 , R 4 、n 1 and n 2 The same symbols as in the above formula (1) have the same meanings.

[0282] In the above formula, R is 5 and R 6 The thermally detachable group is preferred.

[0283] The thermally degradable group is more preferably a thermally degradable group that is degraded at a heating temperature of 230° C. or lower, and further preferably a thermally degradable group that is degraded at a heating temperature of 200° C. or lower.

[0284] Examples of the thermally desorbable group that desorbs at a heating temperature of 200° C. or less include a methoxymethyl group (MOM group) and a tert-butoxycarbonyl group (Boc group).

[0285] Preferred specific examples of the compound (3) include structures represented by the following formulae, but the compound (3) is not limited to these structures.

[0286] [Chemistry 9]

[0287]

[0288] Compound (3) is preferably soluble in the second solvent (particularly ketones such as cyclohexanone, ketone alcohols such as diacetone alcohol, amides such as N-methylpyrrolidone) at room temperature at 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.

[0289] When the solvent solubility is at least the above lower limit, the solubility in the solvent (E), particularly in ketones, ketoalcohols and amides, is excellent, and by using the compound (3), a photosensitive composition excellent in sensitivity and developability can be easily obtained.

[0290] Compound (3) can be produced by the same method as compound (1), for example, the method described in Synthesis Example 1 and Synthesis Example 2 in the following Examples.

[0291] [Example]

[0292] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[0293] [Synthesis Example 1] Synthesis of Lactam Dye (Compound (D-1))

[0294] In a reaction vessel equipped with a cooling tube, 2.00 g of a lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] was added to 10.00 g of N-methylpyrrolidone and dispersed. Subsequently, 1.95 g of di-tert-butyl dicarbonate, 0.11 g of 4-dimethylaminopyridine, and 1.32 g of triethyl orthoformate were added. The obtained solution was heated to 50° C. while stirring under a nitrogen stream, and stirred for 5 hours. Subsequently, the obtained reaction solution was cooled to room temperature and added dropwise to 200 mL of hexane. The generated precipitate was filtered and dissolved in 200 mL of dichloromethane. The obtained dichloromethane solution was washed 3 times with 200 mL of ion exchange 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 target Bk-dye-1 (hereinafter also referred to as "compound (D-1)").

[0295] [Chemistry 10]

[0296]

[0297] [Synthesis Example 2] Synthesis of Lactam Dye (Compound (D-2))

[0298] In a reaction vessel equipped with a cooling tube, 2.00 g of a lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] was added to 10.00 g of N,N-dimethylformamide and dispersed. Subsequently, 0.79 g of chloromethyl methyl ether and 0.21 g of sodium hydride were added, and the obtained solution was heated to 40°C while stirring under a nitrogen stream, and stirred for 16 hours. Subsequently, after the obtained reaction solution was cooled to room temperature, 40 mL of a saturated aqueous sodium bicarbonate solution was added and stirred for 1 hour. The obtained 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 exchange 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 target Bk-dye-2 (hereinafter also referred to as "compound (D-2)").

[0299] [Chemistry 11]

[0300]

[0301] [Synthesis Example 3] Synthesis of Lactam Dye (Compound (D-3))

[0302] In a reaction vessel equipped with a cooling tube, 5 g of indigo carmine 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. Then, the reaction solution was concentrated under reduced pressure using a rotary evaporator and dissolved in 200 mL of ethyl acetate. The ethyl acetate solution was washed 3 times with 200 mL of ion exchange water, and the organic layer was concentrated under reduced pressure using a rotary evaporator and dried under reduced pressure at room temperature to obtain the target 2EH-indigo carmine.

[0303] [Chemistry 12]

[0304]

[0305] 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. Subsequently, 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 injected into 500 mL of isopropanol. The precipitate was then obtained by filtration and then 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)").

[0306] [Chemistry 13]

[0307]

[0308] [Synthesis Example 4] Synthesis of alkali-soluble polymer (A-1)

[0309] In a flask including a cooling tube and a stirrer, 3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of a solvent mixed with equal amounts of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone were placed. In the 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 placed, and nitrogen replacement was performed. Then, stirring was performed slowly, the temperature of the reaction solution was raised to 80°C, and the temperature was maintained for 3 hours to perform polymerization. Then, the temperature of the reaction solution was raised to 100° C., and polymerization was further performed for 1 hour, thereby obtaining an alkali-soluble polymer solution containing 33.3% by mass of a poly(meth)acrylic acid 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.

[0310] [Synthesis Example 5] Synthesis of Alkali-Soluble Polymer (A-2) (Resin Having Acryloyl Group and Carboxyl Group Modified by Acid Anhydride Modification of Cresol Novolac Type Epoxy Acrylate Resin)

[0311] 220 parts by mass of cresol novolac epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220 g / eq.) was placed in a four-necked flask equipped with a stirrer and a reflux cooler, and 214 parts by mass of propylene glycol monomethyl ether acetate was added and heated to dissolve. 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. The mixture was heated to 95°C to 105°C, and 72 parts by mass of acrylic acid was slowly added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80°C to 90°C, 106 parts by mass of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled and taken out to obtain an alkali-soluble polymer solution (solid content concentration: 50% by mass) containing a resin having an acryloyl group and a carboxyl group obtained by modifying a cresol novolac epoxy acrylate resin with anhydride (hereinafter also referred to as "alkali-soluble polymer (A-2)"). The weight average molecular weight (Mw) of the obtained alkali-soluble polymer (A-2) was about 3,500.

[0312] [Synthesis Example 6] Synthesis of Alkali-Soluble Polymer (A-3) (Cage-Type Siloxane Resin)

[0313] With reference to the examples of Japanese Patent Publication No. 2020-184010, a cage-type siloxane resin (hereinafter also referred to as "alkali-soluble polymer (A-3)") was polymerized as described below. 15 g of silsesquioxane (manufactured by Toa Gosei (Co., Ltd., trade name: AC-SQ TA-100) (100 mol% in terms of (meth)acryloyl conversion), 15 g of acetonitrile, and 4.8 g (25 mol%) of 3-mercaptopropionic acid were added to a 200 mL three-necked 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. At this time point, the obtained polymer was confirmed using GPC, and the weight average molecular weight was 4,400, and the residual 3-mercaptopropionic acid in the reaction solution was less than 0.1 mol%, thereby confirming that Michael addition had been carried out quantitatively. After the reaction is completed, move to a separatory funnel, add 100 mL of ethyl acetate, wash once with 100 mL of 1M hydrochloric acid water, and wash three times with 50 mL of water. Then, add 40 g of propylene glycol monomethyl ether acetate (PGMEA) and concentrate until the liquid volume is 40 g, then add 40 g of PGMEA again and concentrate. Then, adjust the solid content concentration to 50% by mass using PGMEA to obtain an alkali-soluble polymer solution containing an alkali-soluble polymer (A-3). The weight average molecular weight of the obtained alkali-soluble polymer (A-3) is 4,400.

[0314] <Evaluation of weight average molecular weight>

[0315] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the prepared polymer are polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0316] Column: TSKgelGRCXLII manufactured by Tosoh Corporation

[0317] Solvent: Tetrahydrofuran

[0318] Temperature: 40℃

[0319] Pressure: 68kgf / cm 2

[0320] [Preparation Example 1] Preparation of Pigment Dispersion (Bk-MB-1)

[0321] 12 parts by mass of a lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] as a colorant, 11.8 parts by mass of BYK-LPN21116 (manufactured by BYK Chemie Japan Co., Ltd., solid content concentration of 40.0% by mass) as a dispersant in terms of solution, 13.0 parts by mass of an alkali-soluble polymer (A-1) as a binder in terms of a polymer solution (solid content concentration of 33.3% by mass), and a mixed solution containing 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 using a bead mill to prepare a pigment dispersion (Bk-MB-1) as a colorant.

[0322] [Preparation Example 2] Preparation of Pigment Dispersion (Bk-MB-2)

[0323] 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 Chemie Japan Co., Ltd., with a solid content concentration of 40.0% by mass) as a dispersant in terms of solution, 13.0 parts by mass of an alkali-soluble polymer (A-1) as a binder in terms of a polymer solution (with a solid content concentration of 33.3% by mass), and a mixed solution containing 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 using a bead mill to prepare a pigment dispersion (Bk-MB-2) as a colorant.

[0324] The details of the colorant, component (A), component (B), component (C), and surfactant used for preparing the photosensitive composition in Examples and Comparative Examples are shown below.

[0325] <Coloring agent>

[0326] D-1: Bk-dye-1 synthesized in Synthesis Example 1 (Compound (D-1))

[0327] D-2: Bk-dye-2 synthesized in Synthesis Example 2 (Compound (D-2))

[0328] D-3: Bk-dye-3 synthesized in Synthesis Example 3 (Compound (D-3))

[0329] Bk-MB-1: the pigment dispersion prepared in Preparation Example 1

[0330] Bk-MB-2: the pigment dispersion prepared in Preparation Example 2

[0331] ODB-2 (manufactured by Yamamoto Chemical Co., Ltd., 3-dibutylamino-6-methyl-7-anilinofluoran)

[0332] <Alkali-soluble polymer (A)>

[0333] A-1: poly(meth)acrylic acid resin synthesized in Synthesis Example 4

[0334] A-2: The resin having an acryloyl group and a carboxyl group synthesized in Synthesis Example 5, wherein the cresol novolac type epoxy acrylate resin is modified with an acid anhydride

[0335] A-3: Cage-type siloxane resin synthesized in Synthesis Example 6

[0336] A-4: "WR-301" manufactured by ADEKA (a PGMEA solution having a solid content concentration of 44% by mass), a resin having an acryloyl group and a carboxyl group obtained by modifying cardo resin with an acid anhydride

[0337] <Polymerizable compound (B)>

[0338] B-1: Dipentaerythritol penta / hexaacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-402)

[0339] <Photopolymerization initiator (C)>

[0340] C-1: Oxime photopolymerization initiator represented by the following formula (C-1):

[0341] C-2: diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate (manufactured by San-Apro Co., Ltd., CPI-100P (photocationic polymerization initiator))

[0342] [Chemistry 14]

[0343]

[0344] <Surfactant>

[0345] F-1: Megafac F-554 (manufactured by DIC Corporation, fluorine-based surfactant)

[0346] [Example 1]

[0347] 12.0 parts by mass of the compound (D-1), 27.0 parts by mass of the alkali-soluble polymer (A-1), 5.0 parts by mass of the polymerizable compound (B-1), 1.0 parts by mass of the photopolymerization initiator (C-1) and 0.1 parts by mass of the surfactant (F-1) were mixed, and then propylene glycol monomethyl ether acetate and cyclohexanone were added in equal amounts so that the solid content concentration of the final composition became 17.0% by mass, followed by stirring to prepare a photosensitive composition.

[0348] In addition, the alkali-soluble polymer (A-1) was used in such a manner that the amount of the alkali-soluble polymer (A-1) in the polymer solution (solid content concentration of 33.3% by mass) obtained in the above-mentioned Synthesis Example 4 was 27.0 parts by mass. In addition, in the test using the alkali-soluble polymer (A-2) or the alkali-soluble polymer (A-3), the polymer solution obtained in the above-mentioned Synthesis Example 5 or Synthesis Example 6 was used in such a manner that the amount of the alkali-soluble polymer (A-2) or the alkali-soluble polymer (A-3) was the numerical value (amount) described in Table 1.

[0349] In the test using Bk-MB-1 or Bk-MB-2, the pigment dispersion prepared in Preparation Example 1 or Preparation Example 2 was used so that the amount of solid content became the numerical value (amount) described in Table 1.

[0350] [Example 2 to Example 8 and Comparative Example 1 to Comparative Example 3]

[0351] A photosensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of each component used were changed as shown in Table 1. In addition, the numerical values ​​in the columns of each component in Table 1 represent parts by mass.

[0352] <Evaluation of photosensitive composition>

[0353] 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.

[0354] <Evaluation of light-shielding properties (transmittance)>

[0355] 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 for preventing sodium ion elution, and then dried under reduced pressure at room temperature to form a coating film with a film thickness of 2.0 μm.

[0356] Then, using MPA-600FA manufactured by Canon Co., Ltd., the photomask was used to conduct the irradiation at 35 mJ / cm 2 The obtained coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of .

[0357] Then, the glass substrate with the exposed coating was placed on a horizontal rotating table of a spin / spray developer (AD-2000, manufactured by Takizawa Industry Co., Ltd.), and a 2.38 mass % tetramethylammonium hydroxide aqueous solution was used for 60 seconds of puddle development at 23° C. Then, the developed substrate was washed with ultrapure water and air-dried, and then post-baked in a clean oven at 230° C. for 30 minutes, thereby forming a 2 cm×4 cm long strip pattern on the substrate.

[0358] The obtained strip pattern was measured for transmittance (optical density (OD) value) when light with a wavelength of 500 nm was incident using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-1900i). The evaluation criteria are as follows. The higher the OD value, the higher the light-shielding property.

[0359] (Evaluation Criteria)

[0360] AA: OD value is above 0.5

[0361] BB: OD value is 0.3 or more and less than 0.5

[0362] CC: OD value is less than 0.3

[0363] <Evaluation of Development Properties>

[0364] Each of the prepared photosensitive compositions was applied onto a soda glass substrate having an indium tin oxide (ITO) film formed on the surface thereof using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a film thickness of 2.0 μm.

[0365] Then, using MPA-600FA manufactured by Canon Co., Ltd., the photomask was used to conduct the irradiation at 35 mJ / cm 2 The coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of .

[0366] Then, the glass substrate with the exposed coating was placed on a horizontal rotating table of a spin / spray developer (AD-2000, manufactured by Takizawa Industry Co., Ltd.), and a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used for 60 seconds of puddle development at 23° C. Then, the developed substrate was washed with ultrapure water and air-dried, and then post-baked in a clean oven at 230° C. for 30 minutes, thereby forming a quadrilateral hole pattern with rounded corners of 5 μm in length and width on the substrate.

[0367] The obtained pattern substrate was subjected to platinum sputtering using 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.), and the number of foreign matter (point-shaped foreign matter) present therein was measured. The evaluation criteria are as follows. The fewer foreign matter there is inside the pattern, the less residue there is during development, that is, the better the developability.

[0368] (Evaluation Criteria)

[0369] AA: The number of foreign objects inside the hole pattern is less than 5

[0370] BB: The number of foreign matter inside the hole pattern is 5 or more and less than 10

[0371] CC: The number of foreign matter inside the hole pattern is 10 or more

[0372] <Evaluation of sensitivity>

[0373] Each of the prepared photosensitive compositions was applied onto a soda glass substrate having an ITO film formed on the surface thereof using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a film thickness of 2.0 μm.

[0374] Next, MPA-600FA manufactured by Canon Co., Ltd. was used, and a photomask capable of forming a line pattern with a line width ranging from 1 μm to 50 μm in units of 1 μm was used. 2 The coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of .

[0375] Then, the glass substrate with the exposed coating was placed on a horizontal rotating table of a spin / spray developer (AD-2000, manufactured by Takizawa Industry Co., Ltd.), and puddle development was performed for 60 seconds at 23° C. using a 2.38% by mass tetramethylammonium hydroxide aqueous solution. Then, the developed substrate was washed with ultrapure water and air-dried, and then post-baked in a clean oven at 230° C. for 30 minutes to form a line pattern.

[0376] The obtained substrate with line pattern is observed with an optical microscope to determine the minimum line width at which the formed line pattern can be formed without defect in the shape corresponding to the photomask. The narrower the minimum line width, the more it indicates that even narrow lines can be fully exposed to the substrate side, a pattern with excellent adhesion to the substrate can be formed, and the sensitivity during exposure is high (the radiation (especially g-ray, h-ray and i-ray) transmittance of the photosensitive composition used is high).

[0377] (Evaluation Criteria)

[0378] AA: minimum line width less than 4μm

[0379] BB: Minimum line width is 4μm or more and less than 6μm

[0380] CC: Minimum line width is 6μm or more

[0381] [Table 1]

[0382]

[0383] <Evaluation of absorbance before and after post-baking at 230°C>

[0384] The photosensitive composition of Example 1 was applied on a soda glass substrate having a SiO2 film formed on the surface for preventing sodium ion elution using a spin coater, and then dried under reduced pressure at room temperature to form a coating film with a thickness of 2.0 μm.

[0385] Then, using MPA-600FA manufactured by Canon Co., Ltd., the photomask was used to conduct the irradiation at 35 mJ / cm 2 The obtained coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of .

[0386] Then, the glass substrate with the exposed coating was placed on a horizontal rotating table of a spin / spray developer (AD-2000, manufactured by Takizawa Industry Co., Ltd.), and a 2.38 mass % tetramethylammonium hydroxide aqueous solution was used for 60 seconds of puddle development at 23° C. Then, the developed substrate was washed with ultrapure water and air-dried, and then heated on a hot plate at 100° C. for 5 minutes, thereby forming a 2 cm×4 cm long strip pattern on the substrate.

[0387] The UV-visible absorbance spectrum of the obtained long strip pattern and the UV-visible absorbance spectrum of the long strip pattern after heating at 230° C. were measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-1900i). The results are shown in Figure 1 . Figure 1 The “protection” spectrum is the spectrum of the long strip pattern before heating at 230°C, and the “deprotection” spectrum is the spectrum of the long strip pattern after heating at 230°C.

[0388] The photosensitive composition of Example 2 containing compound (D-2) was used for measurement. The UV-visible absorbance spectrum of the long strip pattern before and after post-baking at 230°C also showed the same Figure 1 The same behavior was observed in other examples (Example 3 or Examples 4 to 8 including compound (D-3)).

[0389] By introducing a tert-butoxycarbonyl group as a thermally detachable group into the lactam represented by the formula (2) as in the case of the compound (D-1), Figure 1 The absorbance of radiation (i-rays, h-rays) is reduced (transmittance is increased) like the "protection" in the above. Therefore, it is believed that the sensitivity can be improved in Example 1 using compound (D-1) compared to Comparative Examples 1 and 2 prepared using conventional dispersants. By post-baking (calcining) at 230°C after pattern formation, the tert-butoxycarbonyl group of compound (D-1) is decomposed and gasified to restore to the lactam represented by formula (2) with high absorbance before the introduction of the thermally detachable group. Therefore, a cured film with sufficient light-shielding properties can be obtained. The same can be said for compounds (D-2) and (D-3).

[0390] Therefore, in the photosensitive composition using the component (D), by exposing the component (D) to radiation such as i-rays or h-rays in a state where the component (D) is protected by a releasable group, the transmittance of the radiation is high, and the formed coating film can be sufficiently irradiated with light (for example, when the radiation is irradiated from the side opposite to the substrate of the substrate with the coating film, the light is sufficiently irradiated to the coating film on the substrate side), a narrow line can be formed, and pattern residue can be suppressed. In addition, by post-baking at a temperature higher than the temperature at which the releasable group is detached after radiation irradiation and development, the releasable group is detached, and a black cured product with excellent light-shielding properties as the target can be formed.

[0391] As a material that can improve the shielding property after exposure, there are known colorless dyes such as the above-mentioned ODB-2. However, although the OD value of the colorless dye is small before exposure and the transmittance of radiation is high, the OD value is still small after exposure. Even if the colorless dye is used at a concentration of 30% by mass, the OD value increases from 0.1 to about 0.2. The colorless dye cannot form a black cured product with excellent light-shielding properties as the target.

[0392] The lactam pigment [Irgaphor Black S0100CF (manufactured by BASF)] which is a raw material of compound (D-1) and compound (D-2) is almost insoluble in N-methylpyrrolidone, cyclohexanone, diacetone alcohol and propylene glycol monomethyl ether acetate at 25°C.

[0393] On the other hand, the (D) component such as compound (D-1), compound (D-2) and compound (D-3) dissolves at 10% or more by mass relative to each of N-methylpyrrolidone, cyclohexanone and diacetone alcohol at 25°C, and dissolves at 1% or more by mass relative to propylene glycol monomethyl ether acetate at 25°C. In this way, the (D) component has excellent solubility in the solvent, so when the photosensitive composition is prepared using the (D) component, even if the so-called "dispersant" is not used, the desired (uniform) photosensitive composition can be obtained. In the case of forming a hardened material such as a black matrix or a black bank from the photosensitive composition, depending on the purpose of the image display device using the hardened material, it is sometimes required to suppress the adverse effects of other components such as gas escaping, but by using the (D) component with excellent solubility in the solvent, the desired (uniform) photosensitive composition can be obtained even without using a dispersant, and since no dispersant is used, the adverse effects of other components such as gas escaping can be suppressed.

[0394] The above-mentioned Synthesis Examples 1 and 2 can also be regarded as synthesis examples of synthesizing the component (D) which can be called a "dye" by bonding a leaving group to a lactam-based pigment which is called a so-called "pigment".

[0395] By using the component (D) as a "dye" before forming a desired cured product (before post-baking), a photosensitive composition with less foreign matter in the evaluation of developability, less residue during development, and excellent developability was formed compared to Comparative Examples 1 and 2 in which a pigment was used.

[0396] Furthermore, after the releasing group is released by post-baking the component (D) as described above, the component (D) returns to the so-called "pigment", so when a desired cured product (after post-baking) is formed, the cured product contains the "pigment" derived from the component (D).

[0397] If a so-called "dye" is contained in the cured product, the dye may ooze out of the cured product (for example, a black matrix, a black bank) and move to other components such as a light-emitting layer of an image display device or the like using the cured product, which may cause a so-called "dye migration" to adversely affect other components. On the other hand, by post-baking the component (D) as described above, the component contained in the obtained cured product can be made into a "pigment" instead of a "dye", thereby suppressing the above-mentioned dye migration.

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), 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 them is a dissociative group, R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group, n 1 and n 2 Each independently represents an integer of 0 to 4.

2. The photosensitive composition according to claim 1, wherein The leaving group is a methoxymethyl group or a tert-butoxycarbonyl group. 3 . The photosensitive composition according to 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 comprising the hardened material according to claim 4. A black bank comprising the hardened material according to claim 4 .

7. A color filter comprising the black matrix as claimed in claim 5.

8. An image display panel comprising the color filter according to claim 7. 9 . An image display device comprising the image display panel according to claim 8 .

10. An image display device comprising the black bank according to claim 6.

11. A method for manufacturing a hardened object, which is a method for manufacturing a patterned hardened object, and comprises: A step of applying the photosensitive composition according to any one of claims 1 to 3 on a substrate to form a coating film; A step of performing position selective exposure on the coating film; A step of developing the exposed coating film; and A step of heating the developed pattern.

12. The method for producing a cured product according to claim 11, wherein: The patterned hardened material is a black matrix or a black bank.

13. A compound represented by the following formula (3): In formula (3), R 5 and R 6 are each independently a hydrogen atom or a thermally desorbable group that desorbs at a heating temperature of 250° C. or less, and R 5 and R 6 At least one of them is the thermally detachable group, R 3 and R 4 are independently a bromine atom, a chlorine atom, a fluorine atom, an organic group, a nitro group, a carboxyl group or a sulfone group, n 1 and n 2 Each independently represents an integer of 0 to 4.

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