Photosensitive resin composition, cured product, substrate, image display device, and method for producing cured product

Abstract

To provide a photosensitive resin composition capable of forming a coating film that allows active chemical rays to easily pass therethrough and capable of exhibiting a highly shielding black color.SOLUTION: A photosensitive resin composition comprises (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a cured product, a substrate, an image display device, and a method for producing the cured product. [Background technology]

[0002] In panels for display devices such as liquid crystal displays (hereinafter sometimes referred to as "LCD"), components formed from photosensitive compositions, such as interlayer insulating films, planarizing films, and element isolation structures, are used, and patterned light-shielding films such as black matrices (hereinafter sometimes referred to as "BMs") may also be formed. Furthermore, in panels for organic electroluminescence display devices (hereinafter sometimes referred to as "OLED"), a black bank, which is a light-shielding film, may be formed for the purpose of partitioning the light-emitting layer. In order to form a light-shielding film for such applications, various photosensitive compositions containing a light-shielding black pigment and a photopolymerization initiator have been proposed.

[0003] For example, as a positive photosensitive resin composition suitable for forming a light-shielding separator or black matrix of an organic electroluminescent element or a liquid crystal display element, which are flat panel displays, a positive photosensitive resin composition containing (a) an alkali-soluble resin, (b) a quinone diazide compound, (c) a thermochromic compound that develops color upon heating and has an absorption maximum in the range of 350 nm or more and 700 nm or less, and (d) a compound that has no absorption maximum in the range of 350 nm or more and less than 500 nm, and has an absorption maximum in the range of 500 nm or more and 750 nm or less, has been disclosed (see Patent Document 1). The black matrix is ​​formed from a photosensitive composition in which a black pigment such as carbon black or a pigment made black by mixing several kinds of pigments is dispersed, and since a black pigment is used, it has the advantage that it is easy to make it black. For example, Patent Document 2 proposes a black resist composition for forming a black matrix, which contains a black pigment, a photosensitive resin material, and a solvent, and is characterized in that the 20 degree specular gloss of the dried coating film is 100 to 200.

[0004] Meanwhile, in the LCD market, miniaturization is becoming mainstream for tablets, and in the OLED market, the demand for high resolution for large TVs is also increasing. For these reasons, there is a growing demand for high definition BM and black bank. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-326094 A [Patent Document 2] JP 2005-227797 A Summary of the Invention [Problem to be solved by the invention]

[0006] The resists made of the resin compositions disclosed in the above-mentioned Patent Documents 1 and 2 are pre-colored and do not easily allow actinic radiation to pass through during the exposure and development process. This tendency is particularly pronounced when the film has a certain thickness or more in order to obtain high shielding properties. Therefore, the patterning properties are poor, and it has been difficult to achieve high film thickness and thin lines (high aspect ratio).

[0007] In view of the above-mentioned circumstances, an object of the present invention is to provide a photosensitive resin composition that can form a coating film that is easily permeable to actinic rays and that can exhibit a black color with high shielding properties. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by a photosensitive resin composition containing (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent, and have thus completed the present invention. That is, the present invention relates to the following [1] to

[25] .

[0009] [1] A photosensitive resin composition comprising (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent. [2] The photosensitive resin composition according to the above [1], which changes color from a transparent state to a colored state upon heating or exposure to actinic rays. [3] The photosensitive resin composition according to the above [1] or [2], further comprising a photocurable component (E), the photocurable component (E) containing a photopolymerizable monomer (b) and a photopolymerization initiator (c). [4] The photosensitive resin composition according to the above [3], wherein the (c) photopolymerization initiator is a photoradical polymerization initiator. [5] The photosensitive resin composition according to the above [4], wherein the photoradical polymerization initiator is an oxime ester compound. [6] The photosensitive resin composition according to the above [5], wherein the oxime ester compound is an α-ketoxime ester initiator. [7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the (C) acid generator is a photoacid generator. [8] The photosensitive resin composition according to any one of the above [1] to [7], wherein the content of the acid generator (C) relative to the content of the leuco dye (B) is in a molar ratio of (C) / (B)=0.2 or more. [9] A cured product obtained by curing the photosensitive resin composition according to any one of the above [1] to [8].

[10] A substrate having a colored pattern formed from the cured product described in [9] above.

[11] A substrate comprising the cured product according to [9] or

[10] above, and having a colored pattern including both transparent and colored areas.

[12] A substrate comprising a colored pattern made of the cured product according to any one of the above [9] to

[11] , wherein the ratio of the film thickness (h) to the minimum width (w) of the colored portion is h / w≧1.

[13] An image display device comprising the cured product according to any one of the above [9] to

[12] .

[14] A method for producing a cured product using a photosensitive resin composition containing (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent, comprising: (1) a step of applying the photosensitive resin composition to a substrate to form a coating film; (2) a step of subjecting the coating film to a first exposure to actinic rays to obtain an exposed coating film (x); (3) a step of developing the exposed coating film (x) to obtain a developed coating film (X); and (4) a step of heating the coating film (X) to obtain a cured product (z).

[15] A method for producing a cured product according to the above

[14] , comprising the steps (1) to (4) in this order.

[16] A method for producing a cured product according to the above

[15] , comprising, between steps (3) and (4), a step of subjecting the developed coating film (X) to a second exposure using active actinic rays to obtain an exposed coating film (Y) and heating the coating film (Y) to obtain a cured product (Z), or a step of heating the cured product (z) after step (4) to obtain a cured product (Z).

[17] The method for producing a cured product according to any one of the above

[14] to

[16] , wherein the actinic radiation is ultraviolet light.

[18] The method for producing a cured product according to the above

[17] , wherein the actinic radiation is ultraviolet light, and the wavelength of the ultraviolet light in the first exposure is different from the wavelength of the ultraviolet light in the second exposure.

[19] The method for producing a cured product according to any one of the above

[14] to

[18] , wherein the photosensitive resin composition further contains a (E) photocurable component, and the (E) photocurable component contains a (b) photopolymerizable monomer and a (c) photopolymerization initiator.

[20] The method for producing a cured product according to any one of the above

[14] to

[19] , wherein the acid generator (C) is a photoacid generator.

[21] A method for producing a cured product according to any one of the above

[15] to

[20] , comprising, between the steps (2) and (3), a step (2') of subjecting the exposed coating film (x) to a second exposure with active actinic rays to obtain an exposed coating film (y), a step (3) of developing the exposed coating film (y) to obtain a developed coating film (Y), and a step (4) of heating the coating film (Y) to obtain a cured product (Z).

[22] A method for producing a cured product according to any one of the above

[15] to

[21] , comprising a step of subjecting the cured product (z) to a second exposure with activated actinic rays after the step (4) to obtain a cured product (Z), or a step of subjecting the developed coating film (X) to a second exposure with activated actinic rays between the steps (3) and (4) to obtain an exposed coating film (Y).

[23] The method for producing a cured product according to the above

[22] , wherein the actinic radiation is ultraviolet light, and the wavelength of the ultraviolet light in the first exposure is different from the wavelength of the ultraviolet light in the second exposure.

[24] The method for producing a cured product according to any one of the above

[14] to

[23] , wherein the exposed coating film (x) changes color from a transparent state to a colored state by the first exposure.

[25] The method for producing a cured product according to any one of the above

[21] to

[24] , wherein the exposed coating film (x) changes color from a transparent state to a colored state by the second exposure. Effect of the Invention

[0010] According to the present invention, it is possible to provide a photosensitive resin composition which is capable of forming a coating film which is easily permeable to actinic rays and which exhibits a black color with high shielding properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. Note that the following description is an example of an embodiment of the present invention, and the present invention is not limited to these unless it goes beyond the gist of the present invention. In the present invention, "(meth)acrylic" means "either one or both of acrylic and methacrylic". The term "total solids" refers to all components in the photosensitive resin composition other than the solvent. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solids. In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits. In the present invention, the weight average molecular weight means the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, the acid value means an acid value calculated based on the effective solid content, unless otherwise specified, and is calculated by neutralization titration.

[0012] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent. <(A) Resin> The resin that is the component (A) in the photosensitive resin composition of the present invention is not particularly limited as long as it is a polymeric compound capable of forming a coating film, and specific examples thereof include the following compounds. Polyolefin polymers such as polyethylene, polypropylene, and polyisobutylene; diene polymers such as polybutadiene and polyisoprene; polymers having a conjugated polyene structure such as polyacetylene polymers and polyphenylene polymers; vinyl polymers such as polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, poly(meth)acrylic acid, poly(meth)acrylic acid esters, poly(meth)acrylamide, polyacrylonitrile, polymethacrylonitrile, and polyvinylphenol; polyethers such as polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether ether ketone, and polyacetal; novolac resins, olefins, etc. polyesters such as polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resins, and unsaturated polyester resins; polyamides such as nylon-6, nylon 66, water-soluble nylon, and polyphenylene amide; polypeptides such as gelatin and casein; epoxy resins and modified products thereof such as epoxy acrylate resins, novolac epoxy resins, bisphenol epoxy resins, novolac epoxy acrylates, and resins modified with acid anhydrides; polyurethanes, polyimides, melamine resins, urea resins, polyimidazoles, polyoxazoles, polypyrroles, polyanilines, polysulfides, polysulfones, and celluloses.

[0013] Among these resins, resins having a carboxy group or a phenolic hydroxyl group in the side chain or main chain of the resin are preferred from the viewpoint of preventing pollution, since the photosensitive resin composition can be developed in an alkaline state. In particular, resins having a carboxy group include epoxy (meth)acrylate resins, (meth)acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, and polyvinylphenol resins, and among these, epoxy (meth)acrylate resins and (meth)acrylic resins are preferably used from the viewpoint of excellent plate-making properties.

[0014] Epoxy (meth)acrylate resins are resins obtained by reacting the hydroxyl groups produced by the reaction of an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxy group in the ester moiety with a compound having two or more substituents capable of reacting with a hydroxyl group, such as a polybasic acid and / or an anhydride thereof. In addition, the above-mentioned (b1) epoxy (meth)acrylate resin also includes a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group with the above-mentioned polybasic acid and / or anhydride thereof, and then reacting the compound with the polybasic acid and / or anhydride thereof.

[0015] Furthermore, resins obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group that can further react are also included in the above (b1) epoxy (meth)acrylate resin. Thus, epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure, and are not limited to "(meth)acrylate", but are named in this manner according to convention because epoxy compounds (epoxy resins) are the raw material and "(meth)acrylate" is a representative example.

[0016] As the epoxy (meth)acrylate resin, those described in JP-A-2021-135506 are preferably used.

[0017] Examples of the (meth)acrylic resin include copolymers of an ethylenically unsaturated monomer having one or more carboxy groups and another copolymerizable ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers having one or more carboxy groups include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloro(meth)acrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, etc.; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, etc.; mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; p-vinylbenzoic acid, etc. These unsaturated monomers can be used alone or in combination of two or more.

[0018] Other copolymerizable ethylenically unsaturated monomers include, for example, N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

[0019] Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] (meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

[0020] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ] Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; Examples of the polymer include macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. These unsaturated monomers can be used alone or in combination of two or more.

[0021] More specifically, the (meth)acrylic resin described in JP-A-2021-135506 is preferably used.

[0022] In this specification, "(meth)acrylic", "(meth)acrylate", etc. mean "acrylic or methacrylic", "acrylate or methacrylate", etc., for example, "(meth)acrylic acid" means "acrylic acid or methacrylic acid". The weight average molecular weight of these resins measured by GPC is preferably in the range of 1,000 to 100,000. If the weight average molecular weight is 1,000 or more, it is easy to obtain a uniform coating film, and if it is 100,000 or less, the developability is good. The content of the carboxy group is preferably in the range of 5 to 200 in terms of acid value. If the acid value is 5 or more, the resin is soluble in an alkaline developer, and if it is 200 or less, the sensitivity is good.

[0023] <(B) Leuco dye> Leuco dyes are dyes or pigments that can change between two chemical species, one of which is colorless and the other of which is colored, reversibly by heat, light, pH, etc., or irreversibly by oxidation or reduction, and are used as thermal paper inks and pH indicators. In the present invention, a preferred embodiment is to include a leuco dye having such properties in a resin composition and change the color from a transparent state to a colored state by heating or irradiation with activated actinic rays. In the present invention, the transparent state refers to a state in which the absorption of visible light is sufficiently small that the user can judge it to be transparent when looking at it, and more specifically, the absorbance of visible light having a wavelength of 400 nm or more and 800 nm or less is preferably less than 0.1. Also, the colored state refers to a state in which the user can judge it to be colored when looking at it, and more specifically, the absorbance of at least a portion of visible light having a wavelength of 400 nm or more and 800 nm or less is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more. Generally, compounds that have absorption in the visible region have conjugated double bonds or aromatic rings, and therefore many of them have sufficient sensitivity to ultraviolet light and electron beams, which have higher energy than visible light. Therefore, the presence or absence of coloring can be used as an approximate indicator of sensitivity to actinic rays. Leuco dyes generally develop and fade under acidic or alkaline conditions; however, when heated together with a solid acidic developer, the developer and leuco dye melt and develop color as they reach their melting point; when cooled slowly, the developer and leuco dye gradually separate, crystallize, and fade. This makes it possible to control the development and fade of color by temperature. On the other hand, a leuco dye that develops color under acidic conditions immediately reacts with an acid in a photosensitive resin composition or dispersion to develop color, and therefore it is difficult to stably cause a leuco dye and an acidic substance to coexist in a photosensitive resin composition or dispersion. By microencapsulating either or both of the leuco dye and the developer, it is possible to stably mix the two in the photosensitive resin composition or in the dispersion liquid. However, there are technical barriers to microencapsulation and to stably dispersing the microcapsules in the photosensitive resin composition or in the dispersion liquid. By using an acid generator such as a photoacid generator or a thermal acid generator instead of a developer, the acid generator will not decompose and generate acid without a trigger such as light or heat, so it is possible to allow the leuco dye to coexist stably in a transparent state in the photosensitive resin composition or dispersion without using microcapsules.

[0024] (B) The leuco dye is usually basic and is not particularly limited as long as it is a leuco dye that has been conventionally used, and known leuco dyes can be used. Specific examples of the leuco dye include triphenylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, and divinyl leuco dyes, and the like. Fluoran leuco dyes are preferred. The leuco dye (B) changes color upon reaction with an acid generated from the acid generator (C) described below. Representative examples of colorless or light-colored leuco dyes (leuco dye precursors) are shown below. These leuco dyes (leuco dye precursors) may be used alone or in combination of two or more. The (B) leuco dye is used in an amount of preferably 5 to 100 parts by mass, more preferably 8 to 80 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the (A) resin.

[0025] Examples of triphenylmethane leuco dyes include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis(p-dimethylaminophenyl)phthalide [also known as malachite green lactone], and the like.

[0026] Fluoran leuco dyes include 3-diethylamino-6-methylfluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran, 3-diethylamino-6-methyl-7-(o-chloroanilino)fluoran, 3-diethylamino-6-methyl-7-(p-chloroanilino)fluoran. 3-Diethylamino-6-methyl-7-(o-fluoroanilino)fluoran;3-Diethylamino-6-methyl-7-(m-methylanilino)fluoran;3-Diethylamino-6-methyl-7-octylanilinofluoran;3-Diethylamino-6-methyl-7-octylaminofluoran;3-Diethylamino-6-methyl-7-benzylaminofluoran;3-Diethylamino-6-methyl-7-dibenzylaminofluoran;3-Diethylamino-6-chloro-7-methylfluoran;3-Diethylamino-6-chloro -7-Anilinofluoran;3-Diethylamino-6-chloro-7-p-methylanilinofluoran;3-Diethylamino-6-ethoxyethyl-7-anilinofluoran;3-Diethylamino-7-methylfluoran;3-Diethylamino-7-chlorofluoran;3-Diethylamino-7-(m-trifluoromethylanilino)fluoran;3-Diethylamino-7-(o-chloroanilino)fluoran;3-Diethylamino-7-(p-chloroanilino)fluoran;3-Diethylamino-7-(o-fluoroanilino)fluoran Fluoran;3-Diethylamino-benzo[a]fluoran;3-Diethylamino-benzo[c]fluoran;3-Dibutylamino-6-methyl-fluoran;3-Dibutylamino-6-methyl-7-anilinofluoran;3-Dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluoran;3-Dibutylamino-6-methyl-7-(o-chloroanilino)fluoran;3-Dibutylamino-6-methyl-7-(p-chloroanilino)fluoran;3-Dibutylamino-6-methyl-7-(o-fluoroanilino)fluoran;3-Dibutylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran;3-Dibutylamino-6-methyl-chlorofluoran;3-Dibutylamino-6-ethoxyethyl-7-anilinofluoran;3-Dibutylamino-6-chloro-7-anilinofluoran;3-Dibutylamino-6-methyl-7-p-methylanilinofluoran;3-Dibutylamino-7-(o-chloroanilino)fluoran;3-Dibutylamino-7-(o-fluoroanilino)fluoran;3-Di-pentylamino-6-methyl-7-anilinofluoran;3-Di-pentylamino-6-methyl-7-(p-chloroanilino)fluoran;3-Di-pentylamino-7-(m-trifluoromethylanilino)fluoran;3-Di-pentylamino-6-chloro-7-anilinofluoran;3-Di- Pentylamino-7-(p-chloroanilino)fluoran;3-Pyrrolidino-6-methyl-7-anilinofluoran;3-Piperidino-6-methyl-7-anilinofluoran;3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluoran;3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran;3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran;3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran;3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran;3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluoran; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran;3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran;3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluoran;3-Cyclohexylamino-6-chlorofluoran;2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluoran;2-(4-oxahexyl)-3-diethylamino-6 - methyl-7 - anilinofluoran;2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluoran;2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran;2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilinofluoran;2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran;2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran;2-nitro-6-p-(p-diethylaminophenyl)aminoanilinofluoran;2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluoran;2-diethylamino-6-p-(p- diethylaminophenyl)aminoanilinofluoran; 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 2-benzyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluoran; 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluoran; 2,4-dimethyl-6-[(4-dimethylamino)anilino]fluoran and the like.

[0027] Examples of the fluorene-based leuco dye include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide]; 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide]; and the like.

[0028] Examples of divinyl leuco dyes include 3,3-bis[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrabromophthalide; 3,3-bis[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide; 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide; and 3,3-bis[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide.

[0029] Other leuco dyes include 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide; 3,6-bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam; 3, 6-bis(diethylamino)fluoran-γ-(4'-nitro)anilinolactam; 1,1-bis[2',2',2",2"-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-dinitrileethane; 1,1-bis[2',2',2",2"-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoylethane; 1,1-bis[2',2',2",2"-tetrakis(p-dimethylaminophenyl)ethenyl]-2,2-diacetylethane; bis[2,2,2',2'-tetrakis(p-dimethylaminophenyl)ethenyl]-methylmalonic acid dimethyl ester, and the like.

[0030] <Other developers> The photosensitive resin composition of the present invention may contain a developer other than the acid generator (C) as a developer, as long as the effects of the present invention are not impaired. By using another developer, it is possible to obtain a BM and a black bank that are highly resistant to heat, moisture, and water while maintaining high color development sensitivity. Specific examples include bisphenol-based compounds, urea-based compounds, and novolak-type phenol-based compounds. The other color developers may be used alone or in combination of two or more kinds. When the other color developers are used, the amount of the other color developers is preferably 1 to 5,000 parts by mass, more preferably 5 to 1,000 parts by mass, and further preferably 10 to 500 parts by mass, based on 100 parts by mass of the leuco dye (B).

[0031] The bisphenol compounds include 4,4'-isopropylidenediphenol, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, di(4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis(3-tert-octylphenol), 2,2'-thiobis(4-tert-octylphenol), 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, and 4-hydroxy-4-methylpentane. Examples of the bisphenol sulfone derivatives include 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 2,4-bis(phenylsulfonyl)phenol, the bisphenol sulfone crosslinked compounds described in Japanese Patent No. 3913820, and the bisphenol sulfone derivatives described in Japanese Patent No. 4004289.

[0032] Examples of urea compounds include 4,4'-bis(3-(phenoxycarbonylamino)methylphenylureido)diphenylsulfone, N-(p-toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl)urea described in Japanese Patent No. 4601174, 4,4'-bis(3-tosylureido)diphenylmethane described in Japanese Patent Publication No. 2011-105638, and N-[2 -(3-phenylureido)phenyl]benzenesulfonamide, N-[2-(acetoxy)phenyl]-N'-phenylurea, N-[3-(acetoxy)phenyl]-N'-phenylurea, N-[2-(benzoyloxy)phenyl]-N'-phenylurea, N-[3-(benzoyloxy)phenyl]-N'-phenylurea described in JP2017-165091A, Examples of amino acid derivatives include the above-mentioned N-(m-tolylaminocarbonyl)-phenylalanine, N-(p-toluenesulfonyl)-phenylalanine, N-(benzyloxycarbonyl)-valine, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(m-tolylaminocarbonyl)-phenylglycine, N-(m-tolylaminocarbonyl)-valine, N-(m-tolylaminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl)-β-alanine, N-phenylaminothiocarbonyl-glycylglycine, N-(p-toluenesulfonylaminocarbonyl)-phenylalanine-methyl ester, N-(p-toluenesulfonyl)-β-alanine, N-(p-tolylaminocarbonyl)-methionine, and N-(phenylaminocarbonyl)-methionine.

[0033] Examples of the novolak-type phenolic compound include the phenol-formalin condensates described in WO 02 / 098674.

[0034] In addition to the compounds listed above, inorganic acidic substances such as activated clay, attapulgite, colloidal silica, and aluminum silicate, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, aminobenzenesulfonamide derivatives described in JP-A-8-59603, bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4-hydroxyphenylthio)-3-oxapentane, butyl bis(p-hydroxyphenyl)acetate, methyl bis(p-hydroxyphenyl)acetate, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, 1,3-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, and the compounds disclosed in WO 02 / 081229 are also usable. , the compounds described in JP-A-2002-301873, thiourea compounds such as N,N'-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, zinc bis[4-(octyloxycarbonylamino)salicylate] dihydrate, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, and salts of these aromatic carboxylic acids with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, and the like, as well as antipyrine complexes of zinc thiocyanate and complex zinc salts of terephthalaldehydic acid and other aromatic carboxylic acids. Examples of the metal chelate complexes include higher fatty acid metal double salts and polyvalent hydroxy aromatic compounds, as described in JP-A-10-258577.

[0035] Among the above-mentioned other color developers, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4,4'-isopropylidenediphenol, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, diphenyl sulfone crosslinked compounds described in Japanese Patent No. 3913820, diphenyl sulfone derivatives described in Japanese Patent No. 4004289, phenol-formalin condensates described in WO 02 / 098674, 4,4'- Bis(3-(phenoxycarbonylamino)methylphenylureido)diphenyl sulfone, N-(p-toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl)urea described in Japanese Patent No. 4601174, 4,4'-bis(3-tosylureido)diphenylmethane described in Japanese Patent Publication No. 2011-105638, N-[2-(3-phenylureido)phenyl]benzenesulfonamide described in Japanese Patent Publication No. 2016-165835, N-(m-tolylaminocarbonyl)-phenylalanine described in International Publication No. 2017 / 047572, N-(m-tolylaminocarbonyl)-phenylalanine described in International Publication No. 2017 / 047572, Preferred are 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl) sulfone, bisphenol sulfone bridged compounds described in Japanese Patent No. 3913820, bisphenol sulfone derivatives described in Japanese Patent No. 4004289, and N-(p-toluenesulfonyl)-N'-methionine described in Japanese Patent No. 4601174. -(3-p-toluenesulfonyloxyphenyl)urea, 4,4'-bis(3-tosylureido)diphenylmethane described in JP-A-2011-105638, and N-[2-(3-phenylureido)phenyl]benzenesulfonamide described in JP-A-2016-165835 are more preferred.By using these, it is possible to improve image storage stability (heat resistance, plasticizer resistance, moisture resistance, water resistance, grease resistance) while maintaining the color development sensitivity of the heat-sensitive recording material.

[0036] <Sensitizer> In the present invention, a known sensitizer may be used. The sensitizer is not particularly limited, but examples thereof include 1,2-di-(3-methylphenoxy)ethane, 2-benzyloxynaphthalene, fatty acid amides having 10 to 21 carbon atoms (e.g., stearic acid amide, palmitic acid amide, etc.), ethylene bisamide, montanic acid wax, polyethylene wax, p-benzyl biphenyl, diphenyl sulfone, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di(p-chlorobenzyl) oxalate, di(p-methylbenzyl) oxalate, di-p-methylbenzyl oxalate ester, dibenzyl terephthalate, p-benzyl Benzyl oxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis-(phenyl ether), 4-(m-methylphenoxymethyl)biphenyl, 4,4'-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di(3-methylphenoxy)ethylene, bis[2-(4-methoxy-phenoxy)ethyl]ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, p-toluenesulfonamide, and the like can be used. Among these, 1,2-di-(3-methylphenoxy)ethane, 1,2-diphenoxyethane, fatty acid amides having 10 to 21 carbon atoms (e.g., stearic acid amide, palmitic acid amide, etc.), 2-benzyloxynaphthalene, diphenylsulfone, p-toluenesulfonamide, and oxalic acid-di-p-methylbenzyl ester are preferred, and 1,2-di-(3-methylphenoxy)ethane, which shows high color development sensitivity even at low energy, is particularly preferred. These sensitizers may be used alone or in combination of two or more. When a sensitizer is used, the amount of the sensitizer is preferably 25 to 250 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the leuco dye (B).

[0037] <(C) Acid Generator> The acid generator (C) may include a photoacid generator (C1) and a thermal acid generator (C2).

[0038] <<(C1) Photoacid generator>> Photoacid generators are photosensitive agents that decompose when irradiated with active energy rays to generate acid. The generated acid becomes an active species and serves as a catalyst for cationic polymerization, crosslinking reactions, deprotection reactions, etc., and are therefore used as initiators for photocurable resins and in chemically amplified photoresist compositions used in photolithography. Examples of the photoacid generator include onium salt compounds and oxime derivatives having a heteroaryl chromophore.

[0039] Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, and (hydroxyphenyl)benzylmethylsulfonium toluenesulfonate. nate, bis(4-t-butylphenyl)iodonium bis(nonafluorobutanesulfonyl)imide, bis(4-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium bis(trifluoromethanesulfonyl)imide, triphenylsulfonium (octafluorobutane-1,4-disulfonyl)imide, triphenylsulfonium tris(trifluoromethanesulfonyl)methide, t-butyldiphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium Preferred are 1,3-disulfonylhexafluoropropylene imide, triarylsulfonium tetrakis(pentafluorophenyl)borate such as triphenylsulfonium tetrakis(pentafluorophenyl)borate, diaryliodonium tetrakis(pentafluorophenyl)borate such as diphenyltetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium trifluorotris(pentafluoroethyl)phosphate, and the like, and the iodonium cation may be 4-methylphenyl-4'-isobutylphenyliodonium, or 4-methylphenyl-4'-isopropylphenyliodonium. Other examples include JP2002-229192A, JP2003-140332A, JP2002-128755A, JP2003-35948A, JP2003-149800A, JP2002-648 ... These are described in JP2002-116546A, JP2002-156750A, U.S. Patent No. 6,458,506 (US6458506), U.S. Patent Application Publication No. 2003 / 27061 (US2003 / 27061), U.S. Patent No. 5,554,664 (US5,554,664), and WO2007-118794 pamphlet.

[0040] (C1) Examples of the photoacid generator include ionic photoacid generators such as onium salts, such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, and nonionic photoacid generators such as quinone azides, N-oxyimide sulfonates, oxime sulfonates, and iron-allene complexes.

[0041] Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

[0042] Examples of the aromatic iodonium salt include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and the like.

[0043] Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-s[diphenylsulfonio]diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate ... nate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, 4,4'-bis[diphenylsulfonio]diphenyl sulfide bishexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenyl sulfide tetrakis(pentafluorophenyl)borate, and other existing products include Irgacure Examples of such resins include PAG290 (manufactured by BASF), Omnicat 250 (former Irgacure 250), and Omnicat 270 (former Irgacure 270) (all manufactured by IGM Resins BV).

[0044] As the quinone azide photoacid generator, for example, a compound having a phenolic hydroxyl group and a sulfonic acid of naphthoquinone diazide bonded by ester is preferable. The compound having a phenolic hydroxyl group is Bis-Z, BisP-EZ, TekP-TPA, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-p-CR, methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR -OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and other compounds to which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid has been introduced via an ester bond are preferred. Sulfonamide compounds in which naphthoquinone diazide sulfonic acid is bonded to a compound having an amino group can also be used. Compounds other than these can also be used.

[0045] Examples of the N-oxyimide sulfonate photoacid generator include N-(trifluoromethanesulfonyloxy)-5-norbornene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, and the N-oxyimide sulfonates described in JP-A-2013-145383.

[0046] Examples of the oxime sulfonate-based photoacid generator include the oxime sulfonates described in JP-A-2018-505879. The oxime sulfonates are prepared, for example, by reacting the corresponding oxime with a sulfonyl halide, in particular the chloride or anhydride, in an inert solvent, such as t-butyl methyl ether, tetrahydrofuran (THF), dimethoxyethane, dimethylacetamide (DMA) or dimethylformamide, in the presence of a base or a mixture of bases, such as trimethylamine, pyridine or 2,6-lutidine, or in a basic solvent, such as pyridine.

[0047] Examples of the iron-allene complex photoacid generator include xylene-cyclopentadienyliron(II)-hexafluoroantimonate, cumene-cyclopentadienyliron(II)-hexafluorophosphate, and xylene-cyclopentadienyliron(II)-tris(trifluoromethylsulfonyl)methanide.

[0048] Among these, when it is desired to use a photoacid generator that reacts with high sensitivity to a long-wavelength light source, it is preferable to use an aromatic iodonium salt or an aromatic sulfonium salt, and it is particularly preferable to use diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate (San-Apro Co., Ltd., CPI-100P) or diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate (San-Apro Co., Ltd., CPI-101A).

[0049] <<(C2) Thermal acid generator>> A thermal acid generator is a compound that generates an acid when heated, and can reliably polymerize a curable compound in a short time by a polymerization reaction or a crosslinking reaction catalyzed by the generated acid. Thermal acid generators are also excellent in that they have excellent thermal latency and do not impair storage stability. Examples of the thermal acid generator (C2) include ionic thermal acid generators such as onium salts, such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, and non-ionic thermal acid generators such as halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, phosphate compounds, sulfonimide compounds, and sulfonebenzotriazole compounds. From the viewpoint of discoloring the leuco dye (B) in the photosensitive resin composition in an appropriate process, the activation temperature of the thermal acid generator (C2) is preferably 80° C. or higher, and more preferably 90° C. or higher, and is preferably 140° C. or lower, and more preferably 130° C. or lower.

[0050] In the present invention, as described above, the acid generated from the acid generator (C) reacts with the leuco dye (B) to cause a color change. The content of the acid generator (C) is preferably at least 0.2 in terms of molar ratio to the content of the leuco dye (B). When the ratio (C) / (B) is at least 0.2, the amount of acid generated from the acid generator and the content of the leuco dye react just right, allowing efficient discoloration. From the above viewpoints, the ratio (C) / (B) is more preferably at least 1.0, and even more preferably at least 1.2. On the other hand, the upper limit of the ratio (C) / (B) is preferably at most 5.0 from the viewpoint of curability.

[0051] The acid generators (C) may be used alone or in combination of two or more thereof. Also, a photoacid generator (C1) and a thermal acid generator (C2) may be used in combination.

[0052] <(D) Solvent> The (D) solvent has the function of dissolving or dispersing the (A) resin, the (B) leuco dye, the (C) photoacid generator, the (E) photocurable component described below, and other components in the photosensitive resin composition of the present invention, and of adjusting the viscosity. There are no particular limitations on the solvent (D) as long as it can dissolve or disperse each component.

[0053] (D) Solvents include, for example, glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0054] glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0055] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether, and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0056] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride, amyl chloride; Ether ketones such as methoxymethylpentanone; Examples of the solvent include nitriles such as acetonitrile and benzonitrile.

[0057] Examples of commercially available solvents that meet the above criteria include mineral spirits, Barsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (all trade names), etc. These solvents may be used alone or in combination of two or more.

[0058] It is preferable to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure condition of 1013.25 [hPa]. The same applies to all boiling points below.) More preferably, the solvent has a boiling point of 120 to 170°C. Glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc. in the above-mentioned solvents and because the solubility of the components in the composition is relatively high.

[0059] The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent to be used in combination, glycol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is particularly preferred from the viewpoint of solubility of the components in the composition. The ratio of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass, from the viewpoint of solubility.

[0060] It is also preferable to use a solvent having a boiling point of 150°C or more in combination. By using such a high boiling point solvent in combination, the colored resin composition is difficult to dry, but there is an effect of making it difficult for the components in the composition to precipitate due to rapid drying. The content ratio of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass, relative to the (D) solvent. By making it equal to or greater than the lower limit, there is a tendency to easily avoid the coloring material components and the like precipitating and solidifying at the tip of the slit nozzle, for example, causing foreign matter defects, and by making it equal to or less than the upper limit, there is a tendency to easily avoid the drying speed of the composition being slowed down, causing problems such as poor tact in the reduced pressure drying process and pin marks in pre-baking. The solvent having a boiling point of 150° C. or higher may be either a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately add a solvent having a boiling point of 150° C. or higher. Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, triacetin, and the like, among the various solvents mentioned above.

[0061] The content of the (D) solvent in the colored resin composition of the present invention is not particularly limited, but is usually 99% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less. By making it below the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the content of the (D) solvent is usually 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, taking into consideration the viscosity suitable for coating.

[0062] <(E) Photocurable component> The photosensitive resin composition of the present invention preferably contains a photocurable component (E) in addition to the above-mentioned components (A) to (D). The component (E) is preferably a component that is polymerized by active energy rays, and specifically, it preferably contains a photopolymerizable monomer (b) and a photopolymerization initiator (c).

[0063] ((b) Photopolymerizable monomer) The photosensitive resin composition of the present invention preferably contains (b) a photopolymerizable monomer. By containing (b) a photopolymerizable monomer, a strong film can be obtained by photopolymerization, and a strong cured product can be easily obtained. (b) The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound"). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening due to the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. The monomer in the present invention means a concept opposite to the so-called polymeric substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in the narrow sense. In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds that the polyfunctional ethylenic monomer has is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. By making it equal to or more than the lower limit, there is a tendency for high sensitivity to be obtained, and by making it equal to or less than the upper limit, there is a tendency for solubility in a solvent to be improved.

[0064] Examples of the ethylenic compound include unsaturated carboxylic acids and their esters with monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl-containing hydroxy compound.

[0065] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, examples of the acrylic acid moiety of these acrylates include methacrylic acid esters in which the acrylic acid moiety is replaced with a methacrylic acid moiety, itaconic acid esters in which the itaconic acid moiety is replaced with a crotonic acid moiety, and maleic acid esters in which the maleic acid moiety is replaced with a maleic acid moiety.

[0066] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound is not necessarily a single substance, but may be a mixture.Typical examples include a condensate of (meth)acrylic acid, phthalic acid, and ethylene glycol, a condensate of (meth)acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensate of (meth)acrylic acid, adipic acid, butanediol, and glycerin.

[0067] Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and the like, with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane, etc.

[0068] Other useful ethylenic compounds for use in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, a polyfunctional monomer in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and particularly preferably, the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol.

[0069] These monomers may be used alone, but since it is difficult to use a single compound in the production, two or more of them may be used in combination. Furthermore, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, if necessary. The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 100 mgKOH / g, and particularly preferably 5 to 40 mgKOH / g. By setting it to the lower limit or more, there is a tendency that the development dissolution characteristics can be improved, and by setting it to the upper limit or less, there is a tendency that the production and handling are improved and the curing properties such as photopolymerization performance and pixel surface smoothness are easily improved. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to adjust the acid group of the entire polyfunctional monomer to be within the above range.

[0070] In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Also, those described in paragraphs

[0056] and

[0057] of JP-A-2013-140346 can also be used. Furthermore, from the viewpoint of improving the chemical resistance of pixels and the linearity of pixel edges, the polymerizable monomer described in JP-A-2013-195971 can be used. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, the polymerizable monomer described in JP-A-2013-195974 can be used.

[0071] The content ratio of the (b) photopolymerizable monomer in the photosensitive resin composition of the present invention is not particularly limited, but is usually 0 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, and particularly preferably 20 mass% or more, based on the total solid content of the photosensitive resin composition of the present invention, and is usually 80 mass% or less, preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 40 mass% or less, and particularly preferably 30 mass% or less. The ratio relative to 100 parts by mass of the (A) resin is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, and particularly preferably 60 parts by mass or more, and is usually 200 parts by mass or less, preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less. By making it equal to or more than the lower limit, the curability tends to improve, and by making it equal to or less than the upper limit, the development solubility tends to improve.

[0072] ((c) Photopolymerization initiator) In the photosensitive resin composition of the present invention, the (c) photopolymerization initiator is preferably a photoradical polymerization initiator. The photosensitive resin composition is usually prepared by adding a photopolymerization initiator to a polymerizable monomer having an ethylenically unsaturated bond. Such a photosensitive resin composition can be polymerized and cured when irradiated with polychromatic light having wavelengths of, for example, 365 nm, 405 nm, and 436 nm. Examples of photoradical polymerization initiators include benzoin compounds, benzophenone compounds, benzil ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, and oxime ester compounds. Many oxime ester compounds are used as highly sensitive photopolymerization initiators. Many properties of oxime ester compounds are described in several patent documents, and several commercial products related to oxime ester compounds are known. Most of such oxime ester photopolymerization initiators are currently applied to photosensitive resin compositions in the field of LCDs.

[0073] (c) The photopolymerization initiator preferably has a maximum absorption wavelength of 300 nm to 450 nm, more preferably 350 nm to 400 nm, from the viewpoint of being able to fully utilize the energy emitted from the light source and being excellent in productivity. As an initiator having such a maximum wavelength, an oxime ester photopolymerization initiator is preferred.

[0074] The oxime ester photopolymerization initiator generates radicals when irradiated with light. The radicals allow the polymerization of the photopolymerizable monomer to proceed favorably in the deep part of the coating film made of the photosensitive resin composition. In addition, from the viewpoint of proceeding the polymerization reaction in the deep part of the coating film more efficiently, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet light having a wavelength of 350 nm or more. As the photopolymerization initiator that can efficiently utilize ultraviolet light having a wavelength of 350 nm or more, a triazine compound or an oxime ester compound is preferably used, and an oxime ester compound is particularly preferable. Commercially available oxime ester photopolymerization initiators are divided into oxime ester compounds and α-ketoxime ester compounds. Oxime ester compounds generally have a strong absorption wavelength around 365 nm and exhibit high sensitivity, so they are used in photosensitive resin compositions for color filters and photosensitive resin compositions for black matrix. Examples of such oxime ester photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04 (all manufactured by BASF Japan Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA Corporation), and compounds described in JP-A-2022-518535. On the other hand, α-ketoxime ester photopolymerization initiators do not cause a change in the color coordinates of the color resist composition when exposed to ultraviolet light. For this reason, α-ketoxime ester compounds are mainly used in photosensitive resin compositions for color filters, particularly in red, green and blue photosensitive resin compositions. As such α-ketoxime ester photopolymerization initiators, for example, α-ketoxime carbazole derivatives having aroyl and / or heteroaroyl groups, Irgacure OXE-01, and compounds described in JP 2022-518535 A are known.

[0075] The amount of the photopolymerization initiator (c) added is usually 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the photopolymerizable monomer (b). Within the above range, the reaction of the polymerizable group tends to proceed sufficiently.

[0076] Furthermore, the photopolymerization initiator can be made highly sensitive by using a photosensitizer. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene. The photosensitizer can be used alone or in combination of two or more kinds. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the (b) photopolymerizable monomer.

[0077] [Cured product] The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. The curing method is photopolymerization by irradiation with actinic rays. The method for producing the cured product will be described in detail below.

[0078] [Method of manufacturing the cured product] The method for producing the cured product of the present invention uses a photosensitive resin composition containing (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent, and is produced by the following methods (1) to (4). Note that (E) a photocurable component contains (b) a photopolymerizable monomer and (c) a photopolymerization initiator. (1) A step of applying a photosensitive resin composition to a substrate to form a coating film. (2) a step of first exposing the coating film to actinic radiation to obtain an exposed coating film (x) (3) A process of developing the exposed coating film (x) to obtain a developed coating film (X). (4) A process of heating the coating film (X) to obtain a cured product. The components (A) to (E) are as described above.

[0079] The method for producing the cured product of the present invention includes the above steps (1) to (4), and it is particularly preferable to produce the product in the order of steps (1) to (4). Step (1) is a step of applying a photosensitive resin composition to a substrate to form a coating film. The substrate is a transparent substrate included in a display panel of a liquid crystal display device, an organic EL device, or the like, and the material is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin and poly(meth)acrylic resin, and various glasses. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0080] The transparent substrate and the black matrix-formed substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment with a silane coupling agent, or various resins such as urethane resins, as necessary, in order to improve surface properties such as adhesion. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When a thin film formation treatment with various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less. In the present invention, the photosensitive resin composition is applied onto the transparent substrate, and the substrate serves as a substrate on which the BM and black bank are provided by curing the composition. When forming a color filter, a black matrix is ​​provided on the transparent substrate, and then red, green, and blue pixel images are usually formed to produce a color filter.

[0081] The method for forming the coating film is not particularly limited, and may be a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among them, the die coating method is preferable from an overall viewpoint, since it significantly reduces the amount of coating solution used, it is completely free of the influence of mist that adheres when using the spin coating method, and furthermore, it suppresses the generation of foreign matter. If the coating thickness is too thick, pattern development becomes difficult, and if it is too thin, the pigment concentration decreases and sufficient light-shielding properties cannot be obtained. The coating thickness, as the film thickness after drying, is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less.

[0082] In step (2) of the method for producing a cured product, the coating film obtained in step (1) is exposed to actinic radiation for the first time to obtain an exposed coating film (x). In this step, the (B) leuco dye reacts with the acid generated from the (C) acid generator and discolors. In addition, in the case where the (E) photocurable component is contained, the (b) photopolymerizable monomer contained as the photocurable component polymerizes with the radical active species generated by decomposition of the (c) photopolymerization initiator to form a cured product. Examples of the actinic radiation irradiated to the coating film include ultraviolet light, visible light, and electron beams. Since ultraviolet light curing is more productive and requires less equipment cost than electron beam curing, ultraviolet light is preferred as the actinic radiation. The exposure dose can be appropriately selected depending on the content of the photoreaction initiator in the photosensitive resin composition. The wavelength of the ultraviolet light to be irradiated may be selected depending on the type of photopolymerization initiator contained in the photosensitive resin composition.

[0083] The step (3) in the method for producing a cured product is a step of developing the coating film (x) obtained by exposure in the step (2) to obtain a developed coating film (X). The developing step may be positive or negative. The developer for the coating film may be produced by forming an image on the substrate by developing with an aqueous solution containing a solvent or an alkaline compound. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a surfactant, a dye or a pigment.

[0084] Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono-, di-, or triisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more kinds.

[0085] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids.

[0086] Examples of the solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. The solvent may be used alone or in combination with an aqueous solution. The conditions for the development treatment are not particularly limited, but the development temperature is usually 10° C. or higher, preferably 15° C. or higher, and more preferably 20° C. or higher, and usually 50° C. or lower, preferably 45° C. or lower, and more preferably 40° C. or lower. The development method may be any method such as immersion development, spray development, brush development, or ultrasonic development.

[0087] The step (4) in the method for producing a cured product is a step of heating the coating film (X) obtained by development in the step (3) to obtain a cured product (z). In this step, the patterned colored cured film obtained in the step (3) is further cured by thermal polymerization to produce a cured product (z). When the (C) acid generator is a (C2) thermal acid generator, coloring is performed in the step (4).

[0088] The method for producing a cured product of the present invention may include, between the above steps (2) and (3), a step (2') of subjecting the exposed coating film (x) to a second exposure using active actinic rays to obtain an exposed coating film (y). In the case where the (C) acid generator is a (C1) photoacid generator and the (E) photocurable component is included in the negative photosensitive resin composition, the (C1) photoacid generator and (c) photopolymerization initiator absorb the active chemical rays and decompose in the coating film by the first exposure in the above step (2), generating an acid and a radical, respectively. At this time, if the absorption spectra of the (C1) photoacid generator and (c) photopolymerization initiator used overlap to some extent or are close to each other, the generation of chemical species from the (C1) photoacid generator and (c) photopolymerization initiator will occur competitively in balance with the absorbance and cleavage efficiency, and the curing and color development by the generated chemical species will also proceed competitively, which may result in insufficient developability and / or color development. Therefore, by performing the second exposure between the above steps (2) and (3), the amount of generated active chemical species will increase, and the curing and color development will be promoted more than with a single exposure, and the developability and / or color development can be improved. In such a case, a coating film (y) that is more blackened and / or cured is obtained. Here, the actinic radiation for the first exposure and the second exposure is preferably ultraviolet light, but the conditions such as the exposure dose, exposure time, and wavelength of the ultraviolet light may be the same or different. The wavelength of the ultraviolet light may be the same or different in the first exposure and the second exposure, but is preferably different. For example, when the absorption spectra of the (C1) photoacid generator and the (c) photopolymerization initiator do not overlap in the exposure wavelength region, the first exposure is irradiated with ultraviolet light in the absorption wavelength region of the (c) photopolymerization initiator to give priority to curing, and the subsequent second exposure is irradiated with ultraviolet light in the absorption wavelength region of the (C1) photoacid generator to give priority to color development, so that even if the film is thick, color development can be achieved after deep curing, which is excellent for producing a thick coating film.

[0089] The method for producing a cured product of the present invention may include a step (3') between the above steps (3) and (4) of subjecting the developed coating film (X) to a second exposure with active actinic rays to obtain an exposed coating film (Y). In the case of a negative photosensitive resin composition containing the acid generator (C) being the photoacid generator (C1) and the photocurable component (E), the same effect as that obtained by the second exposure between the steps (2) and (3) can be expected. In addition, the degree of curing of the cured product obtained can be increased by further irradiating the developed coating film (X) with actinic rays. When the (C) acid generator is a (C1) photoacid generator and the (E) photocurable component is not contained in the positive-type photosensitive resin composition, the portion colored in step (2) is removed by step (3), but the remaining pattern portion can be colored by the second exposure.

[0090] The method for producing a cured product of the present invention may include a step of subjecting the cured product (z) to a second exposure to actinic rays after the step (4) to obtain a cured product (Z). In the case of a negative-type photosensitive resin composition in which the (C) acid generator is the (C1) photoacid generator and the (E) photocurable component is contained, for example, in the case where the production process of the cured product is carried out in a low temperature region, the obtained cured product can be post-exposed to further increase the blackening and / or the degree of curing. In the case where the (C) acid generator is the (C1) photoacid generator and the (E) photocurable component is not included in the positive photosensitive resin composition, the same effect as that obtained by carrying out the second exposure between the above steps (3) and (4) can be expected. In addition, in the case where the production process of the cured product is carried out in a low temperature region, the degree of blackening can be further increased by post-exposing the obtained cured product.

[0091] [substrate] A substrate having a colored pattern formed on the cured product is also within the scope of the present invention. As described above, the photosensitive resin composition of the present invention is suitably used as a BM material and a black bank material. A specific example of a method for forming a BM or a black bank is a photolithography method, in which a pattern is formed using a mask material during the first exposure and the second exposure described in the above-mentioned method for producing a cured product.

[0092] The BM and black bank thus prepared are colored patterns containing both transparent areas and colored areas colored by exposure to light. From the viewpoint of achieving high definition, it is preferable that the ratio of the film thickness (h) to the minimum width (w) of the colored portion (hereinafter sometimes referred to as the "aspect ratio") is h / w≧1.

[0093] [Image display device] The image display device of the present invention includes the above-mentioned cured product. The above-mentioned cured product is effective for producing a black matrix, and can be suitably used for a color filter having the thus obtained BM. The image display device is not particularly limited, but examples thereof include a liquid crystal display device and an organic EL display device. The cured product of the present invention can be applied to components of image display devices other than the black matrix, such as an interlayer insulating film, a planarizing film, and an element isolation structure. EXAMPLES

[0094] The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Tables 2 and 3 show the components and contents of the photosensitive resin compositions of the comparative examples and examples, as well as the evaluation results.

[0095] Comparative Example 1 (Preparation of Carbon Black Dispersion) Carbon black (SB550, manufactured by Orion Engineered Carbons), dispersant (DB167, manufactured by BYK Japan), dispersion aid (S12000K, manufactured by Lubrizol Corporation) and propylene glycol monomethyl acetate (PGMEA) were mixed in the mass ratios shown in Table 1 below to obtain a mixed solution. Note that the blending ratio of PGMEA in the table below includes the amount of solvent derived from the dispersant and the amount of solvent derived from the dispersion aid. Beads were added to this mixture, and dispersion treatment was carried out for 6 hours at 25 to 45°C using a paint shaker. Zirconia beads with a diameter of 0.5 mm were used, and 2.5 times the mass of the dispersion liquid was added. After dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a carbon black dispersion liquid.

[0096] [Table 1]

[0097] (Preparation of Photosensitive Resin Composition) As shown in Table 2, 14.2 parts by mass of the obtained carbon black dispersion, 26.6 parts by mass of resin (A-1) (ZCR-1798H manufactured by Nippon Kayaku Co., Ltd.), 7.1 parts by mass of a photopolymerizable monomer represented by formula (E-1) and 0.8 parts by mass of a photopolymerization initiator represented by formula (E-2) as photocurable components, 10.0 parts by mass of a surfactant (fluorine-based surfactant F559 manufactured by DIC Corporation), and 41.3 parts by mass of PGMEA (propylene glycol monomethyl acetate) were added and mixed to prepare photosensitive resin composition 3.

[0098] (Evaluation of Photosensitive Resin Composition) The obtained photosensitive resin composition 3 was applied onto a glass substrate by spin coating and dried at 80° C. for 100 seconds to form a film having a thickness of 2 μm. The obtained film was exposed to light of 80 mJ / cm using an ultra-high pressure mercury lamp through a negative mask and a filter for cutting light of 330 nm or less was attached. 2 The light intensity at a wavelength of 365 nm was 45 mW / cm 2 It was. Next, development was carried out with an aqueous solution of potassium hydroxide with a concentration of 0.03%, and the coating film was then baked for 30 minutes at 230° C. Photosensitive resin composition 3 of Comparative Example 1 was colored before exposure because it contained carbon black.

[0099] [Comparative Example 2] (Preparation of Photosensitive Resin Composition) As shown in Table 2, 2.8 parts by mass of the obtained carbon black dispersion, 34.0 parts by mass of resin (A-1) (ZCR-1798H manufactured by Nippon Kayaku Co., Ltd.), 9.1 parts by mass of a photopolymerizable monomer represented by formula (E-1) and 0.8 parts by mass of a photopolymerization initiator represented by formula (E-2) as photocurable components, 10.0 parts by mass of a surfactant (fluorine-based surfactant F559 manufactured by DIC Corporation), and 43.3 parts by mass of PGMEA (propylene glycol monomethyl acetate) were added and mixed to prepare photosensitive resin composition 4.

[0100] (Evaluation of Photosensitive Resin Composition) The obtained photosensitive resin composition 4 was applied onto a glass substrate by spin coating and dried at 80° C. for 100 seconds to form a film having a thickness of 2 μm. The obtained film was exposed to light of 80 mJ / cm using an ultra-high pressure mercury lamp through a negative mask and a filter for cutting light of 330 nm or less was attached. 2 The light intensity at a wavelength of 365 nm was 45 mW / cm 2 Then, development was carried out with an aqueous solution of potassium hydroxide having a concentration of 0.03%, and the coating film was baked for 30 minutes at 230° C. Photosensitive resin composition 4 of Comparative Example 2 was colored before exposure because it contained carbon black.

[0101] [Comparative Example 3] (Evaluation of Photosensitive Resin Composition) The photosensitive resin composition 4 was applied onto a glass substrate by spin coating and dried at 80° C. for 100 seconds to form a film having a thickness of 0.9 μm. The obtained film was exposed to light of 80 mJ / cm using an ultra-high pressure mercury lamp through a negative mask and a filter for cutting light of 330 nm or less was attached. 2 The light intensity at a wavelength of 365 nm was 45 mW / cm 2 Then, development was carried out with an aqueous solution of potassium hydroxide having a concentration of 0.03%, and the coating film was baked for 30 minutes at 230° C. Photosensitive resin composition 4 of Comparative Example 3 was colored before exposure because it contained carbon black.

[0102] The compounds used in the examples and comparative examples are shown below.

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] Example 1 (Synthesis of Resin (A-2)) 145 parts by mass of PGMEA was stirred while replacing with nitrogen, and the temperature was raised to 120° C. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 8.47 parts by mass of 2,2′-azobis-2-methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was changed to air replacement, and 43.2 parts by mass of acrylic acid, 0.7 parts by mass of trisdimethylaminomethylphenol, and 0.12 parts by mass of hydroquinone were added and reacted for 12 hours at 100° C. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted for 3.5 hours at 100° C. The weight average molecular weight Mw of the resin (A-2) thus obtained was measured by GPC to be about 8400, and the acid value was 80 mgKOH / g.

[0109] (Preparation of Photosensitive Resin Composition) As shown in Table 2, 26.8 parts by mass of resin (A-2), 7.2 parts by mass of photopolymerizable monomer represented by formula (E-1) as photocurable component and 0.8 parts by mass of photopolymerization initiator represented by formula (E-2), 4.0 parts by mass of fluoran compound represented by formula (B-1) as leuco dye, 0.8 parts by mass of photoacid generator represented by formula (C-1), and 10.0 parts by mass of surfactant (DIC Corporation, fluorine-based surfactant F559) were added to 50.4 parts by mass of tetrahydrofuran and mixed to prepare photosensitive resin composition 1. This photosensitive resin composition 1 was transparent.

[0110] (Evaluation of Photosensitive Resin Composition) The obtained photosensitive resin composition 1 was applied onto a glass substrate by spin coating and dried at 80° C. for 100 seconds to form a film having a thickness of 2 μm. The obtained film was exposed to light of 80 mJ / cm using an ultra-high pressure mercury lamp through a negative mask and a filter for cutting light of 330 nm or less was attached. 2 The light intensity at a wavelength of 365 nm was 45 mW / cm 2 It was. The coating was then developed with a 0.03% aqueous solution of potassium hydroxide, and then baked at 230° C. for 30 minutes to obtain a cured film. The cured film was black in color.

[0111] [Example 2] (Preparation of Photosensitive Resin Composition) As shown in Table 2, 26.8 parts by mass of resin (A-2), 7.2 parts by mass of photopolymerizable monomer represented by formula (E-1) as photopolymerizable component and 0.8 parts by mass of photopolymerization initiator represented by formula (E-2), 4.0 parts by mass of fluoran compound represented by formula (B-1) as leuco dye, 0.8 parts by mass of photoacid generator represented by formula (C-2), and 10.0 parts by mass of surfactant (DIC Corporation, fluorine-based surfactant F559) were added to 50.4 parts by mass of tetrahydrofuran and mixed to prepare photosensitive resin composition 2. This photosensitive resin composition 2 was transparent.

[0112] (Evaluation of Photosensitive Resin Composition) The obtained photosensitive resin composition 2 was applied onto a glass substrate by spin coating and dried at 80° C. for 100 seconds to form a film having a thickness of 2 μm. The obtained film was exposed to light of 80 mJ / cm using an ultra-high pressure mercury lamp through a negative mask and a filter for cutting light of 330 nm or less was attached. 2 A proxy exposure was made using this. Next, after developing with a 0.03% potassium hydroxide aqueous solution, the film was exposed to light of all wavelengths at an exposure of 80 mJ / cm using an ultra-high pressure mercury lamp, with the filter cutting off light of 330 nm or less removed. 2 The coating was then baked at 230°C for 30 minutes to obtain a cured film. The cured film was black in color.

[0113] [Table 2]

[0114] <Transmittance evaluation> The spectral transmittance of the cured films on the glass substrates obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to evaluate the spectral transmittance at a wavelength of 550 nm.

[0115] <Developability Evaluation Criteria> Those in which the pattern remained after development were rated as ◯, and those in which part of the pattern was peeled off were rated as ×. <Curability evaluation criteria> The pencil hardness of the surface of the cured coating film obtained was measured according to JIS K5600-5-4. A sample with one or less scratches or dents out of five was deemed to pass, and two or more were deemed to fail. The maximum hardness that passed was determined as the pencil hardness.

[0116] [Table 3]

[0117] [Discussion of results] The results are shown in Table 3. From Example 1 in Table 3, it can be seen that a cured film with excellent developability was obtained by using the photosensitive resin composition of the present invention. On the other hand, when the resin compositions containing the carbon black dispersions of Comparative Examples 1 to 3 were used, the developability was insufficient regardless of the degree of shielding property. Moreover, from Example 2, it can be seen that a cured film excellent in developability and curability is obtained by performing two exposures using the photosensitive resin composition of the present invention. In Example 2, although the exposure wavelength region is limited in the first exposure, the resin is exposed to light transparent at the time of irradiation, so that the resin exhibits a curability that is sufficiently resistant to development while being colored, and the second exposure is believed to have ensured the curability of the coating film. In the case of using a photosensitive resin composition containing a carbon black dispersion as in Comparative Examples 1 to 3, it is believed that it is difficult to obtain a good coating film because the developability is further reduced when the exposure wavelength region is limited in the first exposure as in Example 2. As described above, the photosensitive resin composition of the present invention can provide a black cured film with excellent developability, and is particularly useful in a process in which exposure is performed twice, in which the initial exposure energy is reduced to ensure curability by post-exposure.

Claims

1. A photosensitive resin composition comprising (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent.

2. The photosensitive resin composition according to claim 1, which changes color from a transparent state to a colored state upon heating or exposure to actinic rays.

3. 2. The photosensitive resin composition according to claim 1, further comprising: (E) a photocurable component, the (E) photocurable component comprising (b) a photopolymerizable monomer and (c) a photopolymerization initiator.

4. The photosensitive resin composition according to claim 3 , wherein the (c) photopolymerization initiator is a photoradical polymerization initiator.

5. The photosensitive resin composition according to claim 4 , wherein the photoradical polymerization initiator is an oxime ester compound.

6. The photosensitive resin composition according to claim 5, wherein the oxime ester compound is an α-ketoxime ester initiator.

7. The photosensitive resin composition according to claim 1 , wherein the acid generator (C) is a photoacid generator.

8. 2. The photosensitive resin composition according to claim 1, wherein the content of the acid generator (C) relative to the content of the leuco dye (B) is such that the molar ratio (C) / (B) is 0.2 or more.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

10. A substrate comprising a colored pattern formed from the cured product according to claim 9.

11. A substrate comprising the cured product according to claim 9 and having a colored pattern including both transparent and colored areas.

12. A substrate comprising a colored pattern comprising the cured product according to claim 9, wherein the ratio of the film thickness (h) to the minimum width (w) of the colored portion is h / w≧1.

13. An image display device comprising the cured product according to claim 9 .

14. A method for producing a cured product using a photosensitive resin composition comprising (A) a resin, (B) a leuco dye, (C) an acid generator, and (D) a solvent, comprising: (1) A step of applying the photosensitive resin composition to a substrate to form a coating film. (2) a step of first exposing the coating film to actinic radiation to obtain an exposed coating film (x); (3) A step of developing the exposed coating film (x) to obtain a developed coating film (X). (4) A step of heating the coating film (X) to obtain a cured product (z) The method for producing a cured product comprising the steps of:

15. The method for producing a cured product according to claim 14, comprising the steps (1) to (4) in this order.

16. The method for producing a cured product according to claim 15, further comprising, between the steps (3) and (4), a step of subjecting the developed coating film (X) to a second exposure using active actinic rays to obtain an exposed coating film (Y) and heating the coating film (Y) to obtain a cured product (Z), or a step of heating the cured product (z) after the step (4) to obtain a cured product (Z).

17. The method for producing a cured product according to claim 14 or 16, wherein the actinic radiation is ultraviolet radiation.

18. The method for producing a cured product according to claim 17, wherein the actinic radiation is ultraviolet radiation, and the wavelength of the ultraviolet radiation in the first exposure is different from the wavelength of the ultraviolet radiation in the second exposure.

19. The method for producing a cured product according to claim 14, wherein the photosensitive resin composition further contains (E) a photocurable component, and the (E) photocurable component contains (b) a photopolymerizable monomer and (c) a photopolymerization initiator.

20. The method for producing a cured product according to claim 19 , wherein the acid generator (C) is a photoacid generator.

21. The method for producing a cured product according to claim 20, further comprising, between steps (2) and (3), a step (2') of subjecting the exposed coating film (x) to a second exposure with active actinic rays to obtain an exposed coating film (y), a step (3) of developing the exposed coating film (y) to obtain a developed coating film (Y), and a step (4) of heating the coating film (Y) to obtain a cured product (Z).

22. The method for producing a cured product according to claim 20, further comprising a step of subjecting the cured product (z) to a second exposure with active actinic rays after the step (4) to obtain a cured product (Z), or a step of subjecting the developed coating film (X) to a second exposure with active actinic rays between the steps (3) and (4) to obtain an exposed coating film (Y).

23. The method for producing a cured product according to claim 22, wherein the actinic radiation is ultraviolet radiation, and the wavelength of the ultraviolet radiation in the first exposure is different from the wavelength of the ultraviolet radiation in the second exposure.

24. The method for producing a cured product according to claim 19, wherein the exposed coating film (x) changes color from a transparent state to a colored state by the first exposure.

25. The method for producing a cured product according to claim 21 or 22, wherein the exposed coating film (x) changes color from a transparent state to a colored state by the second exposure.

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