Photosensitive resin composition for black resist, manufacturing method thereof, light-shielding film, color filter, touch panel, and display device

Abstract

This invention provides a photosensitive resin composition for black resist, its manufacturing method, a light-blocking film, a color filter, a touch panel, and a display device. The photosensitive resin composition for black resist can form highly detailed patterns, significantly reduce reflectivity, and suppress the formation of aggregated foreign matter. A photosensitive resin composition for black resist comprises: (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable compound having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-blocking component selected from the group consisting of black pigment, mixed pigments, and light-blocking materials, (E) inorganic particles, and (F) a dispersant. When the interaction radius of component (F) is set as R... 0, when the distance between each component or dispersion and the Hansen solubility parameter of component (F) is set as Ra, Ra / R The RED value represented by 0 satisfies a specific condition.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition for a black resist, a method for manufacturing the photosensitive resin composition, a light-shielding film formed by curing the photosensitive resin composition, a color filter having the light-shielding film and a touch panel, and a display device having the color filter or the touch panel. Prior Technology

[0002] In recent years, due to the development of mobile devices, there has been an increase in display devices with touch panels or liquid crystal panels used in outdoor or vehicle applications. In these display devices, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back, and a light-shielding film (black matrix) is provided on the liquid crystal panel to suppress light leakage from the screen when displaying black and to suppress the mixing of adjacent color resists.

[0003] In display devices and the like, to suppress light leakage and improve the visibility of the screen, the concentration of black pigment in the light-shielding film is sometimes increased to improve the light-shielding properties (reduce the light transmittance of the light-shielding film). Compared to the refractive index of the transparent substrate or the curing resin, the refractive index of the black pigment is higher. Therefore, if the concentration of black pigment in the light-shielding film is increased, the reflectivity will increase when viewed from the side of the transparent substrate opposite to the side where the light-shielding film is formed. Consequently, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, resulting in an undesirable situation where the black matrix boundary is prominent due to reflections onto the light-shielding film or differences in reflectivity with the colored portion of the color filter.

[0004] Therefore, there is an urgent need for a black photosensitive resin composition for resisting that can produce a light-shielding film with both high light-shielding properties and low reflectivity.

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition characterized by comprising: hydrophobic silica particles and a specific dispersant (urethane-based dispersant). By using the hydrophobic silica particles and the specific dispersant, a black matrix that balances high opacity and low reflectivity can be formed. [Existing Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2015-161815 Summary of the Invention

[0007] [The problem the invention aims to solve] However, the inventors conducted research and found that the black photosensitive resin composition described in Patent Document 1 has the following problems: burrs are generated at the edge of the pattern during pattern formation, or the reflectivity is not reduced as expected, or aggregated foreign matter originating from silicon dioxide particles is generated on the black matrix.

[0008] The present invention is made in view of the above aspects, and its object is to provide a black photosensitive resin composition for photoresist capable of forming high-precision patterns, sufficiently reducing reflectivity and suppressing the generation of foreign matter, a light-shielding film formed by curing the black photosensitive resin composition for photoresist, a color filter having the light-shielding film and a touch panel, and a display device having the color filter or the touch panel. [Technical means to solve the problem]

[0009] One aspect of the present invention relates to a black photosensitive resin composition for photoresist described below [1] to [7]. [1] A photosensitive resin composition for a black resist, comprising: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) Select at least one light-blocking component from the group consisting of black pigments, mixed pigments, and light-blocking materials; (E) Inorganic particles with a refractive index of 1.10 or higher and 1.80 or lower; and (F) Dispersant, Regarding component (A), the dispersion of component (D), the dispersion of component (E), and component (F), When the radius of Hansen's dissolution sphere, i.e. the interaction radius of the (F) component, is set to R0, When the distance between the Hansen solubility parameters of each component or dispersion and the Hansen solubility parameter of component (F) is set as Ra, The relative energy difference (RED) value between each component or dispersion and component (F), represented by Ra / R 0, satisfies the following condition. The RED value between component (A) and component (F) is less than 1.00 MPa 1 / 2. The RED value between the dispersion of component (D) and component (F) is less than 0.51 MPa 1 / 2. The RED value between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2. [2] The photosensitive resin composition for black resist according to [1], wherein the (A) photosensitive resin containing unsaturated groups is a photosensitive resin containing unsaturated groups obtained by reacting an epoxy compound of the following general formula (1) having two glycidyl ether groups derived from bisphenols with (meth)acrylic acid, and then with a polycarboxylic acid or its anhydride. [Chemistry 1] (In formula (1), R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and a halogen atom, respectively; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, the fusiform-9,9-dimethyl or single bond represented by general formula (2), and l is an integer from 0 to 10) [Chemistry 2] [3] The photosensitive resin composition for black resist according to [1] or [2], wherein the RED value between the dispersion of the (D) component and the (F) component is less than 0.40 MPa 1 / 2. [4] A black photosensitive resin composition for photoresist according to any one of [1] to [3], wherein the difference (HSP-RED value) between the dispersion of the (E) component and the (F) component is less than 0.85 MPa 1 / 2. [5] A photosensitive resin composition for a black resist according to any one of [1] to [4], wherein the difference (HSP-RED value) between the dispersion of the (E) component and the (F) component is 0.85 MPa 1 / 2 or more and less than 2.00 MPa 1 / 2. [6] A black photosensitive resin composition for photoresist according to any one of [1] to [5], wherein the dispersion of the (E) component comprises a dispersant. [7] A photosensitive resin composition for a black resist according to any one of [1] to [6], wherein the (E) component is an inorganic particle selected from the group consisting of silicon dioxide particles, aluminum oxide particles and magnesium fluoride particles.

[0010] Another aspect of the present invention relates to a method for manufacturing a black photosensitive resin composition for photoresist described below [8] to

[10] . [8] A method for manufacturing a photosensitive resin composition for a black photoresist, comprising: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) A dispersion of an opaque component formed by dispersing at least one opaque component selected from the group consisting of black pigment, mixed pigment, and opaque material in a solvent; (E) An inorganic particle dispersion formed by dispersing inorganic particles in a solvent; and (F) Dispersant, in the manufacturing method Regarding component (A), the dispersion of component (D), the dispersion of component (E), and component (F), Select the dispersions of component (A), (D), (E), and (F) as follows: When the radius of Hansen's dissolution sphere, i.e. the interaction radius of the (F) component, is set to R0, When the distance between the Hansen solubility parameters of each component or dispersion and the Hansen solubility parameter of component (F) is set as Ra, The relative energy difference (RED value) between each component or dispersion and component (F), represented by Ra / R 0, satisfies the following condition. The RED value between component (A) and component (F) is less than 1.00 MPa 1 / 2. The RED value between the dispersion of component (D) and component (F) is less than 0.51 MPa 1 / 2. The RED value between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2. [9] The method for manufacturing a photosensitive resin composition for a black resist according to [8], wherein the dispersion of the (E) component comprises a dispersant.

[10] The method for manufacturing a photosensitive resin composition for a black resist according to [8] or [9], wherein the dispersion of the (E) component is a dispersion of inorganic particles selected from the group consisting of alumina particles and magnesium fluoride particles.

[0011] Another aspect of the present invention relates to a light-shielding film as described below

[11] .

[11] A light-shielding film is formed by curing a black resist according to any one of [1] to [7] with a photosensitive resin composition.

[0012] Another aspect of the present invention relates to a color filter as described below

[12] .

[12] A color filter having a black matrix as described in

[11] as a light-shielding film.

[0013] Another aspect of the present invention relates to a touch panel as described below

[13] .

[13] A touch panel having a light-shielding film according to

[11] .

[0014] Another aspect of the present invention relates to a display device as described below

[14] ,

[15] .

[14] A display device having a color filter according to

[12] .

[15] A display device having a touch panel according to

[13] . [The effects of the invention]

[0015] The present invention provides a black photosensitive resin composition for photoresist capable of forming highly detailed patterns, sufficiently reducing reflectivity, and suppressing the generation of foreign matter; a light-shielding film formed by curing the black photosensitive resin composition for photoresist; a color filter having the light-shielding film and a touch panel; and a display device having the color filter or the touch panel. Implementation

[0016] Hereinafter, a detailed description of one embodiment of the present invention will be provided. The photosensitive resin composition for black resist according to one embodiment of the present invention (hereinafter, simply referred to as "photosensitive resin composition") comprises: (A) a photosensitive resin containing unsaturated groups; (B) a photopolymerizable compound having at least two or more unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-blocking component selected from the group consisting of black pigment, mixed pigment, and light-blocking material; (E) inorganic particles with a refractive index of 1.10 or higher and 1.80 or lower; and (F) a dispersant. Hereinafter, components (A) to (F) will be described.

[0017] 1.(A)Ingredients (A) is a photosensitive resin containing unsaturated groups. (A) preferably contains a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. There are no particular limitations on the resin in question, and it can be widely used.

[0018] Examples of photosensitive resins containing unsaturated groups include epoxy (meth)acrylate acid adducts obtained by reacting (meth)acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter also referred to as "bisphenol-type epoxy compounds represented by general formula (1)") to obtain a compound having hydroxyl groups, and then reacting a polycarboxylic acid or its anhydride with the obtained compound having hydroxyl groups. The term "epoxide compound derived from bisphenols" refers to an epoxy compound or equivalent obtained by reacting bisphenols with epihaloalcohols. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, referring to one or both of these.

[0019] The epoxy (meth)acrylate acid adduct is preferably a bisphenol type epoxy compound represented by the following general formula (1).

[0020] [Chemistry 3]

[0021] (In formula (1), R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and a halogen atom, respectively; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, the fusiform-9,9-dimethyl or single bond represented by general formula (2), and l is an integer from 0 to 10)

[0022] [Chemistry 4]

[0023] The bisphenol type epoxy compound represented by general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. In the reaction, oligomerization of diglycidyl ether compounds is generally involved, thus including epoxy compounds containing more than two bisphenol backbones.

[0024] Examples of bisphenols used in the reaction include: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl) benzoyl, bis(4-hydroxy-3,5-dimethylphenyl) benzoyl, bis(4-hydroxy-3,5-dichlorophenyl) benzoyl, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy- 3,5-Dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl)propane 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) fumonisin, 9,9-bis(4-hydroxy-3-methylphenyl) fumonisin, 9,9-bis(4-hydroxy-3-methylphenyl) fumonisin, 9,9-bis(4-hydroxy-3-methylphenyl) fumonisin (4-hydroxy-3-chlorophenyl) bisphenol, 9,9-bis(4-hydroxy-3-bromophenyl) bisphenol, 9,9-bis(4-hydroxy-3-fluorophenyl) bisphenol, 9,9-bis(4-hydroxy-3-methoxyphenyl) bisphenol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) bisphenol, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) bisphenol, 9,9-bis(4-hydroxy-3,5-dibromophenyl) bisphenol, 4,4'-biphenyl, 3,3'-biphenyl, etc. Among these, bisphenols containing bisphenol-9,9-diyl group are preferred.

[0025] Furthermore, examples of monoanhydrides of (a) dicarboxylic acids or tricarboxylic acids that react with the hydroxyl groups in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include: monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids include: monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, octanoic acid, and diethylene glycol. Examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include: monoanhydrides of cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornane dicarboxylic acid. In addition, examples of monoanhydrides of aromatic dicarboxylic or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, and trimellitic acid. Any substituents may be introduced into these monoanhydrides of dicarboxylic or tricarboxylic acids.

[0026] Furthermore, examples of dianhydrides of (b) tetracarboxylic acids that react with epoxy (meth)acrylates include: dianhydrides of chain-type tetracarboxylic acids, alicyclic tetracarboxylic acids, and aromatic tetracarboxylic acids. Examples of dianhydrides of chain-type tetracarboxylic acids include: butanetetracarboxylic acids, pentanetetracarboxylic acids, and hexanetetracarboxylic acids. Examples of dianhydrides of alicyclic tetracarboxylic acids include: cyclobutanetetracarboxylic acids, cyclopentanetetracarboxylic acids, cyclohexanetetracarboxylic acids, cycloheptanetetracarboxylic acids, and norbornanetetracarboxylic acids. Examples of dianhydrides of aromatic tetracarboxylic acids include: pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and diphenyl ethertetracarboxylic acid. Any substituent may be introduced into the dianhydrides of these tetracarboxylic acids.

[0027] The molar ratio (a) / (b) of the monoanhydride of (a) dicarboxylic acid or tricarboxylic acid and the dianhydride of (b) tetracarboxylic acid reacting with epoxy (meth)acrylate is preferably 0.01 or more and 10.0 or less, more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) is within the aforementioned range, it is easy to obtain the optimal molecular weight for preparing a photosensitive resin composition with good photopatterning properties. Furthermore, there is a tendency that the larger the molar ratio (a) / (b), the smaller the molecular weight and the higher the alkali solubility.

[0028] The reaction of epoxy compounds with (meth)acrylic acid, and the reaction of epoxy (meth)acrylates obtained by means of said reaction with polycarboxylic acids or their anhydrides, are not particularly limited and can be carried out by known methods.

[0029] Other examples of resins preferred as component (A), i.e., photosensitive resins containing unsaturated groups, include: resins that are copolymers of (meth)acrylic acid, (meth)acrylates, etc., and have (meth)acrylic acid and carboxyl groups. Examples of such resins include alkali-soluble resins containing polymerizable unsaturated groups obtained by: copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting (meth)acrylic acid with the obtained copolymer, and finally reacting a dicarboxylic acid or tricarboxylic acid anhydride. The copolymer may refer to: the copolymer disclosed in Japanese Patent Application Publication No. 2014-111722, which comprises 20 mol% to 90 mol% repeating units derived from glycerol ester, which is obtained by esterifying the hydroxyl groups at both ends of (meth)acrylic acid, and 10 mol% to 80 mol% repeating units derived from one or more polymeric unsaturated compounds that can copolymerize therewith, and has a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 mgKOH / g to 120 mgKOH / g; and the polymer disclosed in Japanese Patent Application Publication No. 2018-141968, which comprises units derived from (meth)acrylate compounds and units having (meth)acrylic acid and dicarboxylic acid residues or tricarboxylic acid residues, has a weight average molecular weight (Mw) of 3000 to 50000, and an acid value of 30 mgKOH / g to 200 mgKOH / g, i.e., an alkali-soluble resin containing polymeric unsaturated groups.

[0030] The weight-average molecular weight (Mw) of component (A) is preferably 2000 or more and 10000 or less. Furthermore, the acid value of component (A) is preferably 30 mgKOH / g or more and 200 mgKOH / g or less. The weight-average molecular weight (Mw) of the photosensitive resin containing unsaturated groups can be determined, for example, using a gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). Regarding the acid value, it can be determined by dissolving the resin solution in dioxane, for example using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) and titrating with a 1 / 10 N-KOH aqueous solution.

[0031] (A) Components may be used alone or in combination with two or more. The content of component (A) relative to the total mass of the solid components is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less.

[0032] 2. (B) Component (B) Component is a photopolymerizable compound having two or more unsaturated bonds. Examples of component (B) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxy-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylate esters, as well as dendritic polymers having (meth)acrylate groups as compounds having vinyl double bonds, etc. Only one of these photopolymerizable compounds can be used alone, or two or more can be used in combination. Component (B) can function to crosslink the molecules of component (A) with each other; from the viewpoint of more fully utilizing the aforementioned function, it is preferable to use a photopolymerizable compound having three or more unsaturated bonds. Furthermore, the acrylate equivalent obtained by dividing the molecular weight of the photopolymerizable compound by the number of (meth)acrylate groups in one molecule is preferably 50 to 300, and more preferably 80 to 200. In addition, component (B) does not have a free carboxyl group.

[0033] Examples of dendritic polymers having a (meth)acrylic group include dendritic polymers obtained by adding a portion of the carbon-carbon double bond in the (meth)acrylic group of a polyfunctional (meth)acrylate to a multi-thiol compound. Specifically, this includes dendritic polymers obtained by reacting the (meth)acrylic group of a polyfunctional (meth)acrylate represented by the following general formula (3) with a multi-thiol compound represented by the following general formula (4).

[0034] [Chemistry 5]

[0035] (In formula (3), R5 is a hydrogen atom or a methyl group, and R6 is the residual portion after n hydroxyl groups of the k hydroxyl groups of R7(OH)k are added to the ester bond in the formula. Preferably, R7(OH)k is a polyol with a non-aromatic straight-chain or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyol ether formed by the dehydration condensation of multiple molecules of the polyol and the linkage via an ether bond, or an ester of these polyols or polyol ethers with a hydroxy acid. k and n independently represent integers from 2 to 20, k ≧ n)

[0036] [Chemistry 6]

[0037] (In formula (4), R8 is a single bond or a hydrocarbon group with 1 to 6 carbon atoms in the divalent to hexavalent state, and m is 2 when R8 is a single bond, and is the same number as the valence of R8 when R8 is a divalent to hexavalent group.)

[0038] Examples of polyfunctional (meth)acrylates represented by general formula (3) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone modified pentaerythritol tri(meth)acrylate, etc. These compounds may be used alone or in combination with two or more.

[0039] Examples of polythiol compounds represented by general formula (4) include: trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thioglycolate), pentaerythritol tetras (thioglycolate), pentaerythritol tris (thioglycolate), pentaerythritol tetras (thioglycolate), dipentaerythritol hexas (thioglycolate), and dipentaerythritol hexas (thioglycolate). These compounds may be used alone or in combination with two or more.

[0040] The mixing ratio of component (A) to component (B), by mass ratio (A) / (B), is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20. If the mixing ratio of component (A) is 30 / 70 or higher, the cured product after photocuring is less likely to become brittle. Furthermore, the acid value of the coating in the unexposed area is less likely to decrease, thus suppressing a decrease in solubility relative to the alkaline developer. Therefore, defects such as burrs at the pattern edges or dullness are less likely to occur. Additionally, if the mixing ratio of component (A) is 90 / 10 or lower, the proportion of photoreactive functional groups in the resin is sufficient, thus allowing for the formation of the desired cross-linked structure. Furthermore, since the acid value of the resin component is not too high, the solubility of the exposed area relative to the alkaline developer is less likely to increase, thus suppressing the formation of a pattern that is thinner than the target line width or pattern defects.

[0041] 3. (C) Component (C) Component is a photopolymerization initiator. Furthermore, the term "photopolymerization initiator" in this specification is used in the sense that it includes sensitizers.

[0042] Examples of ingredients (C) include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and other acetophenone derivatives; benzophenone, 2-chlorobenzophenone, p,p'-bis(dimethylaminobenzophenone), and other benzophenone derivatives; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; and biimidazole derivatives such as 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole. Compounds; halogenated methylthiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl) 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and other halomethyl-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylmercaptophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylmercaptophenyl)butane-1,2-dione-2-oxime-O-acetate, O-Acetic oxime compounds such as 1-(4-methylmercaptophenyl)butane-1-ketooxime-O-acetate and 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-gazo-3-yl-O-acetylated oxime; sulfur compounds such as benzopyrene dimethyl ketal, thioxanthones, 2-chlorothioxanthones, 2,4-diethylthioxanthones, 2-methylthioxanthones, and 2-isopropylthioxanthones; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine.These photopolymerization initiators can be used alone, or in combination of two or more.

[0043] Of these, component (C) is preferably an O-acyloxime compound-based (including ketoxime) photopolymerization initiator. Because O-acyloxime compound-based photopolymerization initiators have high sensitivity, sufficient photosensitivity can be ensured even when the content of the light-shielding material (D) is high, thus significantly improving the developability (resolution) of the hardened film.

[0044] Examples of O-acetylgime compound photopolymerization initiators include those represented by general formula (5) or general formula (6).

[0045] [Chemistry 7]

[0046] (In formula (5), R9 and R10 independently represent alkyl groups with 1 to 15 carbon atoms, aryl groups with 6 to 18 carbon atoms, arylalkyl groups with 7 to 20 carbon atoms, or heterocyclic groups with 4 to 12 carbon atoms, respectively, and R11 represents alkyl groups with 1 to 15 carbon atoms, aryl groups with 6 to 18 carbon atoms, or arylalkyl groups with 7 to 20 carbon atoms. Here, alkyl and aryl groups can be substituted with alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, or halogens, and the alkylene part can contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. In addition, the alkyl group can be any type of straight-chain, branched, or cyclic alkyl group.)

[0047] [Chemistry 8]

[0048] (In formula (6), R12 and R13 are independently linear or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl having 4 to 10 carbon atoms, or phenyl groups that can be substituted with alkyl groups having 1 to 6 carbon atoms. R14 are independently linear or branched alkyl or alkenyl groups having 2 to 10 carbon atoms, and a portion of the -CH2- group in the alkyl or alkenyl group can be substituted with an -O- group. Furthermore, a portion of the hydrogen atoms in these R12 to R14 groups can also be substituted with halogen atoms.)

[0049] Furthermore, component (C) preferably has a molar absorptivity of 10,000 L / mol·cm or higher at 365 nm. Because of its high sensitivity, this photopolymerization initiator ensures sufficient photosensitivity even in photosensitive resin compositions containing a large acrylic equivalent of component (B), thus significantly improving the developability (resolution) of the photosensitive resin composition. Examples of such photopolymerization initiators include: Omnirad 1312 (manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company), and ADEKA ARKLS NCI-831 (manufactured by ADEKA Inc., "ADEKA ARKLS" is a registered trademark of the company), etc.

[0050] In this specification, the molar absorptivity of the photopolymerization initiator can be set as the value obtained by measuring the absorbance of a 0.001% by mass acetonitrile solution in a quartz unit with an optical path length of 1 cm using a UV-Vis-IR spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.).

[0051] Furthermore, while it does not function as a photopolymerization initiator or sensitizer on its own, it can be used in combination with the aforementioned compounds to add compounds that enhance the ability of photopolymerization initiators or sensitizers. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of such amine compounds include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc.

[0052] When the total amount of components (A) and (B) is set to 100 parts by mass, the amount of component (C) is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 4 parts by mass or more and 25 parts by mass or less, and even more preferably 4 parts by mass or more and 15 parts by mass or less. If the proportion of component (C) is 3 parts by mass or more, the sensitivity is good, and sufficient photopolymerization speed can be achieved. If the proportion of component (C) is 30 parts by mass or less, moderate sensitivity can be achieved, thus obtaining the desired pattern linewidth and the desired pattern edge.

[0053] 4. (D) Component (D) consists of black pigments, mixed organic pigments, and light-blocking materials. If (D) is a component with an average particle size of 1 nm to 1000 nm (the average particle size measured using a laser diffraction / scattering particle size analyzer or a dynamic light scattering particle size analyzer), then known light-blocking components may be used without particular restriction.

[0054] Examples of black pigments include: perylene black, cyanine black, aniline black, lactone black, carbon black, titanium black, etc.

[0055] Examples of the mixed organic pigments include: pigments composed of at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethyl alkali pigments, phthalocyanine pigments, quinacridone pigments, isoindolineone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinoline phthaloline pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

[0056] Depending on the function of the target photosensitive resin composition, component (D) can be used alone or in combination with two or more components.

[0057] Furthermore, examples of organic pigments that can be used when using mixed organic pigments as component (D) include, but are not limited to, pigments with the following numbers in the Color Index. Pigment Red (2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.) Pigment orange (5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.) Pigment yellow (1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.) Pigment green (7, 36, 58, etc.) Pigment blue in ratios of 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and 80. Pigment violet (19, 23, 37, etc.)

[0058] Of these, black pigment is preferred, and carbon black is even better.

[0059] The average primary particle size of carbon black is preferably 5 nm or more and 60 nm or less, more preferably 10 nm or more and 50 nm or less, and even more preferably 20 nm or more and 45 nm or less. In this specification, the particle size or average primary particle size of the light-shielding component refers to the arithmetic mean of the average of the major and minor axes obtained by observing the light-shielding component using an electron microscope, relating to 1500 particles or primary particles of the light-shielding component. A larger average primary particle size of carbon black makes it easier to disperse at high concentrations. By setting the average primary particle size of carbon black to a moderate size, poor shape of secondary particles or reduction in surface roughness can be suppressed.

[0060] Furthermore, the preferred oil absorption capacity of carbon black is 100 ml / 100 g or less for dibutyl phthalate (DBP). DBP oil absorption capacity refers to the amount of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (Japanese Industrial Standards (JIS) K 6217-4 (2017)). If the DBP oil absorption capacity of the carbon black is within the aforementioned range, the resistivity and blackness of the cured film can be further improved, and the decrease in coatability caused by the high viscosity of the photosensitive resin composition can be suppressed.

[0061] Furthermore, the pH value of carbon black is preferably above 2 and below 10, more preferably above 5 and below 9, and even more preferably above 4 and below 8. The pH value refers to the value obtained by measuring a mixture of carbon black and distilled water using a glass electrode pH meter. The higher the pH value of the carbon black, the greater its stability. By setting the pH value of the carbon black within a reasonable range, the adhesion of the cured film to the substrate can be further improved.

[0062] In addition, the ash content of carbon black is preferably below 1.0%. If the ash content is below 1.0%, the resistivity of the hardened film can be further improved.

[0063] Furthermore, the specific surface area of ​​carbon black is preferably 20 m² / g or higher and 300 m² / g or lower. If the specific surface area is 20 m² / g or higher, the shape of the hardened film is easily stabilized. If the specific surface area is 300 m² / g or lower, the amount of dispersant or dye required can be reduced, thus further reducing costs.

[0064] Furthermore, carbon black preferably has acidic functional groups on its surface obtained through oxidation treatment. More preferably, it has two or more acidic functional groups on its surface obtained through multiple oxidation treatments. These acidic functional groups can improve the dispersibility of the carbon black. Examples of such oxidation treatments include treatments using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, sulfuric anhydride, fluorine gas, concentrated sulfuric acid, nitric acid, and various peroxides. Examples of such acidic functional groups include: hydroxyl, side-oxygen, hydroperoxy, carbonyl, carboxyl, peroxycarboxylic acid, aldehyde, ketone, nitro, nitrosyl, amide, amide, sulfonic acid, sulfinic acid, hyposulfonic acid, thiocarboxylic acid, chloroacetyl, chloroacetyl, perchloroacetyl, iodoacetyl, and iodoacetyl.

[0065] In addition, component (D) can also be surface-treated by dye coating. In particular, carbon black coated with dye can improve the developability of the photosensitive resin composition, and improve the adhesion, fine line reproduction, and light-shielding properties of the hardened film formed by curing the photosensitive resin composition to the substrate, as well as increase the resistivity of the hardened film.

[0066] The dye can be any dye that can be adsorbed onto the surface of the light-blocking component, and can be a basic dye, acid dye, direct dye, reactive dye, etc. Furthermore, when acidic functional groups are imparted to the surface of the light-blocking component (especially carbon black) to improve its dispersibility (through oxidation treatment), an acid dye (especially an acid dye having sulfonic acid or carboxyl groups) that readily interacts with the acidic functional groups is preferred. Additionally, from the viewpoint of suppressing the reaction with the acidic groups present in component (A), an acid dye or a nonionic dye is preferred compared to dyes having amine groups, etc. Furthermore, from the viewpoint of further improving the light-blocking properties of the hardened film, a dark-colored dye is preferred.

[0067] Specific examples of the dyes include: food black No. 1, food black No. 2, food red No. 40, food blue No. 1, food yellow No. 7, and other food coloring dyes; Bernal Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, Basacid Blue 750 (manufactured by BASF), and Bernal Red (Bemcolors, Poughkeepsie, New York). Acid dyes of various colors, including BASF Basacid Black SE 0228 (manufactured by BASF); Pontamine Brilliant Bond Blue A and other Pontamine (registered trademark) dyes (manufactured by Bayer Chemicals Corporation, Pittsburgh, PA); Cartasol Yellow GTF Presscake (manufactured by Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon); Direct Brilliant Pink B (manufactured by Crompton & Knowles). Knowles (manufactured by Sandoz, Inc.) 2GT, Carta Black (manufactured by Sandoz, Inc.)Direct dyes include: Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz), Pergasol Yellow CGP (Ciba-Geigy), Pyrazol Black BG (JCI), Diazol Black RN Quad (JCJ), Pontamine Brilliant Bond Blue, Berncolor AY 34, etc.; Cibaclon Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 4), etc. Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA and similar Levafix (registered trademark) LP dyes (manufactured by Pylam Products, Inc., Tempe, AZ) 56, Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA and similar Levafix (registered trademark) LP dyes.Dyes manufactured by Charlotte, NC, North Carolina; reactive dyes such as Procion Red H8B (Reactive Red 31) (manufactured by JCI America); Neozapon Red 492 (manufactured by BASF); Orasol Red G (manufactured by Ciba-Geigy); Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company); Spirit Fast Yellow 3G; Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company); Orasol Black RL (manufactured by Ciba-Geigy); Orasol... Oil-soluble dyes such as Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), and Morfast Black Concentrate A (manufactured by Morton-Thiokol) are available. These can be used alone or in combination of two or more.

[0068] Relative to the total mass of component (D), the dye content is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less. A higher dye content increases the resistivity of the hardened film. By setting the dye content to a moderate level, thickening of the photosensitive resin composition caused by excess dye and agglomeration caused by excess dye hindering the dispersibility of other components can be suppressed.

[0069] Alternatively, the dye can also be laked using a metal or a metal salt. By laked the dye, the dye is fixed to the surface of the light-shielding component via the metal or metal salt, thus suppressing the reduction in the effect caused by the dye detaching from the surface of the light-shielding component. Examples of metals include aluminum, magnesium, calcium, strontium, barium, and manganese. Examples of metal salts include hydrochlorides and sulfates of these metals. The content of the metal or metal salt relative to the dye is preferably 0.3 moles or more, more preferably 0.5 moles, and even more preferably 0.8 moles.

[0070] Furthermore, the ratio (mE / mD) of the total mass of component (E) (inorganic particles) to the total mass of component (D) (light-shielding component) is preferably 0.01 or more and 0.20 or less, more preferably 0.05 or more and 0.10 or less. If the ratio of the total mass of (E) inorganic particles (mE) to the total mass of (D) light-shielding component (mD) is within the aforementioned range, both high light-shielding performance and low reflectivity can be achieved.

[0071] Component (D) is typically mixed with other formulation components as a dispersion of the opaque component dispersed in a solvent. At this time, dispersants can be added as other formulation components to promote the dispersion of component (D) or to stabilize its dispersion. The dispersant used in the dispersion of component (D) can be any known compound used in the dispersion of pigments (opaque components) (compounds commercially available under names such as dispersant, wetting agent, dispersion accelerator, etc.). Alternatively, a dispersion resin other than a dispersant can be used, within a range that does not impede dispersion stability. Furthermore, even in a photosensitive resin composition, the dispersion of component (D) dispersed using these other formulation components (dispersions, etc.) can be used as a dispersion of component (D) to distinguish it from other components, and its composition can be determined by identifying it as a component with a specific Hansen solubility parameter (HSP) value.

[0072] Examples of dispersants used in the dispersion of component (D) include: cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersion aids). The dispersant is preferably a cationic polymeric dispersant having cationic functional groups such as imidazole, pyrrole, pyridinyl, primary amine, secondary amine, or tertiary amine as adsorption sites for the colorant. Furthermore, the amine value of the cationic polymeric dispersant is preferably 1 mgKOH / g or more and 100 mgKOH / g or less. Additionally, the number average molecular weight (Mn) of the cationic polymeric dispersant is preferably 1000 or more and 100,000 or less. The amount of dispersant prepared relative to the total mass of the opaque component is preferably 1% by mass or more and 35% by mass or less, more preferably 2% by mass or more and 25% by mass or less.

[0073] The amount of component (D) can be arbitrarily determined according to the desired opacity. It is preferably 20% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 70% by mass or less, relative to the total mass of the solid components in the photosensitive resin composition. When using organic pigments such as aniline black, cyanine black, or acetylene black, or carbon-based opacifying components such as carbon black as the opacifying component (D), it is particularly preferably 40% by mass or more and 60% by mass or less, relative to the solid components in the photosensitive resin composition. If the amount of opacifying component is 20% by mass or more, sufficient opacity can be obtained. If the amount of opacifying component is 80% by mass or less, the content of the photosensitive resin that acts as a binder will not decrease, thus obtaining the desired developing characteristics and film-forming ability.

[0074] Furthermore, the content of component (D) in this specification is the amount based on the surface-treated component (D) when the surface is treated with a dye or the like. On the other hand, the content of component (D) is an amount that has minimal impact on opacity and does not include the other formulation components (dispersants, etc.). Furthermore, regarding the Hansen solubility parameter (HSP) described later, since dispersibility is taken into account, the value is used for a dispersion of component (D) containing the other formulation components (dispersants, etc.).

[0075] 5. (E) Component Inorganic particles used as component (E) may include alumina, silicon dioxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, sodium metasilicate, and magnesium fluoride. Among these, silicon dioxide particles, alumina particles, and magnesium fluoride particles are particularly preferred.

[0076] The type of component (E) is not particularly limited; it can be solid or hollow particles. Furthermore, "hollow particles" refers to particles with cavities inside. Additionally, there are no particular restrictions on the manufacturing method (gas-phase reaction, liquid-phase reaction) or shape (spherical, non-spherical) of component (E). Metal oxide particles that have undergone surface treatment using coupling agents, etc., can also be used.

[0077] (E) component can reduce the refractive index of the light-shielding film formed by hardening the photosensitive resin composition.

[0078] In addition, component (E) can suppress reflection caused by the difference in refractive index between the transparent substrate and the formed light-shielding film, so reflection can be suppressed even if an anti-reflective film is not set on the substrate.

[0079] The average particle diameter of the inorganic particles is preferably 10 nm or more and 1000 nm or less, more preferably 10 nm or more and 300 nm or less. Specifically, the average particle diameter of the silicon dioxide particles is preferably 10 nm or more and 150 nm or less, more preferably 20 nm or more and 140 nm or less, and even more preferably 20 nm or more and 130 nm or less. It is believed that, compared with the case of small particle diameters such as several nanometers (nm), when the particle diameter is within the aforementioned range, it is less likely for silicon dioxide particles to aggregate. Therefore, within the particle diameter range, the dispersion stability of silicon dioxide particles is excellent, and thus they can exist uniformly within the light-shielding film. Therefore, the reflectivity of different parts of the surface of the light-shielding film is less likely to deviate. The average particle diameter of the alumina particles is preferably 10 nm or more and 300 nm or less, more preferably 50 nm or more and 250 nm or less, and even more preferably 55 nm or more and 250 nm or less. The average particle size of magnesium fluoride particles is preferably above 10 nm and below 300 nm.

[0080] The average particle diameter of the inorganic particles can be determined using a particle size analyzer called "FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) based on dynamic light scattering, and by using the accumulation method.

[0081] The refractive index of the silica particles is 1.10 or higher and 1.47 or lower. For example, ordinary silica particles (refractive index 1.45 to 1.47) can be used, or hollow silica particles with a low refractive index can be used, thereby reducing the refractive index of the light-shielding film compared to that containing only ordinary silica particles. Furthermore, the refractive index of hollow silica particles is generally not lower than 1.10. The refractive index of the alumina particles is 1.50 or higher and 1.80 or lower. Preferably, it is 1.55 or higher and 1.75 or lower. The refractive index of the magnesium fluoride particles is 1.38 or higher and 1.43 or lower. Inorganic particles can be particles with a refractive index near the midpoint between the transparent substrate and the light-shielding component, as it is believed that by using these particles, the refractive index difference between the glass and the hardened film decreases, thus reducing reflectivity.

[0082] The refractive index of inorganic particles can be determined by mixing a transparent mixture obtained by processing the inorganic particles into powder and a standard refractive liquid with a known refractive index. Alternatively, the refractive index of the inorganic particles can be measured using an Abbe refractometer.

[0083] The inorganic particles can be spherical or elliptical, but are preferably spherical to facilitate a reduction in refractive index and an increase in the strength of the light-shielding film. For example, the sphericity of the inorganic particles is preferably between 1.0 and 1.5. If the sphericity of the inorganic particles falls within this range, the particle shape is close to spherical. Therefore, they can be homogeneously filled into light-shielding films of varying thicknesses, forming a light-shielding film that maintains the smoothness of the film surface while preventing the inorganic particles from protruding from the film surface. Thus, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0084] The sphericity of the inorganic particles can be determined by the ratio of the longest diameter to the shortest diameter of the particles (the average of any 100 silicon dioxide particles). Here, the longest and shortest diameters of the inorganic particles are obtained by photographing the inorganic particles using a transmission electron microscope and measuring the longest and shortest diameters of the inorganic particles based on the obtained microscope images.

[0085] Furthermore, there are no particular limitations on the manufacturing method of inorganic particles; they can be manufactured using known methods such as gas-phase reaction or liquid-phase reaction.

[0086] Component (E) can be mixed with other formulation components as a dispersion of inorganic particles dispersed in a solvent. At this time, a dispersant can be added as another formulation component to promote the dispersion of component (E) or to stabilize its dispersibility. The dispersant can be any known compound used in the dispersion of pigments (opaque components) (compounds commercially available under names such as dispersant, dispersant wetting agent, dispersion accelerator, etc.). Alternatively, a dispersion resin other than a dispersant can be used, provided it does not impede dispersion stability. Furthermore, even in a photosensitive resin composition, the dispersion of component (E) dispersed using these other formulation components (dispersions, etc.) can be used as a dispersion of component (E) to distinguish it from other components, and its composition can be determined by identifying it as a component with a specific HSP value.

[0087] When inorganic particles are premixed with other components, the content of other components is preferably 0.1% by mass or more and 15% by mass or less relative to the total mass of inorganic particles.

[0088] Relative to the total mass of the photosensitive resin composition containing component (G) (solvent), the content of component (E) is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less. If the content of inorganic particles is within the aforementioned range, good photopatternability can be ensured while achieving low reflectivity.

[0089] Furthermore, the content of component (E) in this specification is an amount that has little effect on the refractive index and does not include the other components (dispersants, etc.). On the other hand, for the Hansen solubility parameter (HSP) described later, since dispersibility is taken into account, the value is used for a dispersion containing component (E) that includes the other formulation components (dispersants, etc.).

[0090] 6.(F)Ingredients Component (F) is a dispersant. Component (F) is mainly used to improve the dispersibility of component (E) and exists in the photosensitive resin composition by adsorption onto component (E). According to the present invention, it is believed that a portion of component (F) is also adsorbed onto component (D), which also contributes to improving the dispersibility of component (D). Furthermore, component (F) is different from the dispersant contained in the dispersion of component (D) or the dispersion of component (E) (the dispersant prepared before mixing components (A) to (F), which is a dispersant formulated during the mixing of these components to adjust the dispersion of each component (mainly component (E)). Depending on the timing of the addition, component (F) may be adsorbed onto components (D) and (E) (or also onto component (A)), or the adsorption form may differ from the dispersant contained in the dispersion of component (D) or the dispersion of component (E) (for example, the dispersant contained in these dispersions may be more difficult to detach due to dispersion treatment using a ball mill or the like). In these respects, component (F) may contain a different dispersant than the dispersion of component (D) or the dispersion of component (E).

[0091] Furthermore, it is believed that even in a hardened film formed by curing the photosensitive resin composition, the adsorption state of component (F) on each of the components can be maintained.

[0092] Component (F) primarily improves the dispersibility of component (E) (the dispersion). Here, it is assumed that the higher the compatibility between the other components in the photosensitive resin composition and the dispersion of component (E), the better the dispersibility of component (E). However, even if a dispersant with high compatibility with component (A) (a photosensitive resin containing unsaturated groups), which is abundant in the photosensitive resin composition, is used as component (F) to improve the dispersibility of component (E), the dispersibility of component (E) cannot be sufficiently improved. Sometimes, burrs may occur at the pattern edges due to the agglomerated inorganic particles. Furthermore, the localized presence of light-blocking components may sometimes result in insufficient reduction of reflectivity. Therefore, even if a dispersant with high compatibility with the dispersion of component (E) and high compatibility with the dispersion of component (D) is used as component (F) in order to improve the codispersibility of the dispersion of component (D) and the dispersion of component (E), burrs may still occur at the edge of the pattern, or aggregates of foreign matter originating from inorganic particles may be generated on the black resist.

[0093] Based on these insights, the inventors have repeatedly studied the matter and found that, in order to suppress the occurrence of the aforementioned problems, it is important to consider the compatibility between the dispersions of components (A), (D), and (E) and component (F), and that the preferred range for each component or dispersion differs in terms of the compatibility between the components or dispersions and component (F).

[0094] Specifically, by using a component that satisfies all of the following conditions as component (F), the generation of burrs and aggregates at the edge of the pattern can be suppressed, and the reflectivity can also be sufficiently reduced. The RED value between component (A) and component (F) is less than 1.00 MPa 1 / 2. The RED value between the dispersion of component (D) and component (F) is less than 0.51 MPa 1 / 2. The RED value between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2.

[0095] Here, the so-called RED value is the relative energy difference of the system obtained from the Hansen solubility parameters, and is expressed as Ra / R0. Ra is the distance between the Hansen solubility parameters (HSP) of each component or dispersion and the Hansen solubility parameters (HSP) of component (F). R0 is the interaction radius of component (F).

[0096] The Hansen solubility parameter (HSP) is represented by three parameters: dispersion force, dipole interaction, and hydrogen bond. Furthermore, the dispersion force term in the Hansen solubility parameter of a component or dispersion X is denoted as δDx, the dipole interaction term as δPx, and the hydrogen bond term as δHx. The coordinates of component or dispersion X in the three-dimensional Hansen space are defined as (δDx, δPx, δHx). Similarly, the dispersion force term in the Hansen solubility parameter of another component or dispersion Y is denoted as δDy, the dipole interaction term as δPy, and the hydrogen bond term as δHy. The coordinates of component or dispersion Y in the three-dimensional Hansen space are defined as (δDy, δPy, δHy). In this case, the distance Ra between component or dispersion X and component or dispersion Y is defined as a value expressed by the following formula.

[0097] [Formula 1]

[0098] The Hansen solubility parameter (HSP) of a certain component or dispersion is determined as follows. First, when multiple solvents with known Hansen solubility parameters (dispersion force term, dipole interaction term, and hydrogen bonding term) are mixed with the component or dispersion, the solvents containing the component or dispersion (good solvents) and the solvents containing the component or dispersion (bad solvents) are determined. Then, the Hansen solubility parameters of each solvent are plotted in Hansen space, and a minimum virtual sphere (Hansen's dissolution sphere) containing the good solvent on the inside and the bad solvent on the outside is defined. The center coordinates of Hansen's dissolution sphere are set as the HSP of the component or dispersion. Furthermore, the radius of Hansen's dissolution sphere for component (F) is R0 (interaction radius).

[0099] Furthermore, the HSP of each component or dispersion can be calculated from the chemical structure and quantity of each component or dispersion using known methods. Alternatively, it can be calculated using the Hansen Solubility Parameters in Practice (HSPiP), which is a procedure for determining HSP.

[0100] The RED value, represented by Ra / R0, indicates the compatibility between the components or dispersions. A lower predicted RED value indicates higher compatibility between the components or dispersions. However, according to the novel insights of the present invention, it is not sufficient to select component (F) to uniformly improve the compatibility between all components or dispersions (i.e., to make the HSP of all components or dispersions equally small), but rather that there are optimal RED values ​​relative to the dispersions of components (A), (D), and (E), respectively.

[0101] The RED value between component (A) and component (F) is 1.00 MPa 1 / 2 or less, preferably 0.80 MPa 1 / 2 or less. There is no particular limitation on the lower limit of the RED value between component (A) and component (F), but it can be set to 0.10 MPa 1 / 2 or more, preferably 0.30 MPa 1 / 2 or more.

[0102] The RED value between the dispersion of component (D) and component (F) is 0.51 MPa 1 / 2 or less, preferably 0.40 MPa 1 / 2 or less. There is no particular limitation on the lower limit of the RED value between the dispersion of component (D) and component (F), but it can be set to 0.10 MPa 1 / 2 or more, preferably 0.30 MPa 1 / 2 or more.

[0103] The RED value between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2, preferably less than 0.85 MPa 1 / 2, and more preferably less than 0.50 MPa 1 / 2. There is no particular limitation on the lower limit of the RED value between the dispersion of component (E) and component (F), but it can be set to 0.10 MPa 1 / 2 or more, preferably 0.30 MPa 1 / 2 or more.

[0104] Furthermore, according to the present invention, by lowering the RED value between the dispersion of component (E) and component (F) (e.g., less than 0.85 MPa 1 / 2), the generation of burrs and aggregates at the pattern edges can be suppressed, and the reflectivity can also be sufficiently reduced. On the other hand, by finely adjusting the dispersibility of the dispersion of component (E) within a suitable range that is neither too high nor too low, the generation of burrs and aggregates at the pattern edges can also be suppressed. For example, the RED value between the dispersion of component (E) and component (F) can be set to 0.85 MPa 1 / 2 or higher and 2.00 MPa 1 / 2 or lower, or 1.05 MPa 1 / 2 or higher and 1.45 MPa 1 / 2 or lower.

[0105] Examples of components (F) include: alkyl ammonium salts and alkyl alcohol ammonium salts of acidic polymers, or alkyl ammonium salts and alkyl alcohol ammonium salts of polymers having acid groups, neutralizing salts of polymers having alkylamine groups, phosphate ester salts of polymers, etc. Among these, alkyl ammonium salts of acidic polymers or alkyl ammonium salts of polymers having acid groups are preferred. By using alkyl ammonium salts or alkyl alcohol ammonium salts of acidic polymers, or alkyl ammonium salts or alkyl alcohol ammonium salts of polymers having acid groups as dispersants, the generation of aggregated foreign matter originating from inorganic particles can be more significantly suppressed.

[0106] Furthermore, examples of commercially available dispersants as component (F) include: DISPERBYK-140, 142, 145, 167, 2001, 2025, and 9076 (all manufactured by BYK-Chemie Japan, and "DISPERBYK" is a registered trademark of the company). Among these commercially available products, DISPERBYK-140, 142, 167, and 9076 are preferred, and DISPERBYK-167 and 9076 are even more preferred. Moreover, component (F) may be the same dispersant used in the dispersion of component (D) or the dispersion of component (E), but as described above, it is also possible to distinguish component (F) from the dispersants contained in each dispersion.

[0107] The content of (F) dispersant is preferably 0.05% to 5% by mass relative to the total solids content of the photosensitive resin composition.

[0108] 7. Solvent Preferably, the photosensitive resin composition of the present invention includes, in addition to components (A) to (F), a solvent ((G) component). Examples of solvents include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By using these alone or in combination of two or more, a homogeneous solution can be prepared.

[0109] In addition, the photosensitive resin composition of the present invention may be formulated with resins other than component (A) such as epoxy resin, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than inorganic particles, leveling agents, defoamers, surfactants, coupling agents and other additives as needed.

[0110] Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenolic compounds. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber and mica. Examples of defoamers or leveling agents include: silicone-based, fluorinated, and acrylic compounds. Examples of surfactants include fluorinated surfactants and silicone-based surfactants. Examples of coupling agents include: 3-(glycidoxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, and 3-ureopropyltriethoxysilane.

[0111] The photosensitive resin composition of the present invention preferably comprises, excluding the solvent, a photosensitive resin containing unsaturated groups as component (A), a photopolymerizable compound having at least two or more unsaturated bonds as component (B), a photopolymerization initiator as component (C), at least one light-blocking component selected from the group consisting of black pigments, mixed pigments, and light-blocking materials as component (D), inorganic particles, and a dispersant (F). The amount of solvent varies depending on the target viscosity, and is preferably 40% to 90% by mass relative to the total amount.

[0112] Regarding the photosensitive resin composition of the present invention, a photosensitive resin composition for a black resist can be manufactured by mixing (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-blocking component dispersed in a solvent to form a dispersion of light-blocking components, and (E) an inorganic particle dispersion dispersed in a solvent. The dispersion of component (D) can be prepared by mixing component (D) with other arbitrarily added components (dispersants, etc.) using a ball mill or the like. The dispersion of component (E) can be prepared by mixing component (E) with other arbitrarily added components (dispersants, etc.) using a ball mill or the like.

[0113] Furthermore, the light-shielding film formed by curing the photosensitive resin composition of the present invention can be obtained, for example, by coating a solution of the photosensitive resin composition onto a substrate or the like, drying the solvent, and then curing it by irradiating it with light (including ultraviolet light, radiation, etc.). If a light-irradiated portion and a non-light-irradiated portion are provided using a photoresist or the like, and only the light-irradiated portion is cured, while the other portions are dissolved using an alkaline solution, the desired pattern can be obtained.

[0114] Furthermore, the light-shielding film of the present invention can be used as a color filter or touch panel of a black matrix, for example, by forming a light-shielding film with a thickness of 1.0 μm to 2.0 μm on a transparent substrate, forming red, blue and green pixels using photolithography after the light-shielding film is formed, and injecting red, blue and green inks into the light-shielding film using an inkjet process.

[0115] Furthermore, the light-shielding film formed by curing the photosensitive resin composition of the present invention can also be used as a black columnar spacer in a liquid crystal display device. For example, multiple portions with different film thicknesses can be made using a single black resist, with one portion functioning as a spacer and another functioning as a black matrix.

[0116] Specific examples are given for each step of the film-forming method for coating / drying a light-shielding film based on a photosensitive resin composition.

[0117] As a method for coating a photosensitive resin composition onto a substrate, any known method can be used, such as solution impregnation, spraying, or using a roller coater, land coater, slot coater, or rotary coater. After coating to the desired thickness using these methods, the solvent is removed (pre-baking), thereby forming a film. Pre-baking is performed by heating using an oven, hot plate, or vacuum drying, or a combination thereof. The heating temperature and time during pre-baking can be appropriately selected depending on the solvent used; for example, it is preferably performed at 80°C to 120°C for 1 to 10 minutes.

[0118] The radiation used in the exposure can be, for example, visible light, ultraviolet light, far-ultraviolet light, electron beams, X-rays, etc., with a wavelength range preferably between 250 nm and 450 nm. Additionally, suitable developing solutions for alkaline development include, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developing solutions can be appropriately selected based on the characteristics of the resin layer, but adding surfactants as needed is also effective. The preferred developing temperature is 20°C to 35°C, allowing for the precise formation of fine images using commercially available developing machines or ultrasonic cleaners. Furthermore, water washing is typically performed after alkaline development. As developing methods, spray developing, immersion developing, and puddle developing methods can be applied.

[0119] After development, the light-shielding film is heat-treated (post-baked) at 180°C to 250°C for 20 to 100 minutes. This post-baking is performed to improve the adhesion between the patterned light-shielding film and the substrate. Similar to pre-baking, it can be performed using an oven, hot plate, or similar heating method. The patterned light-shielding film of the present invention is formed through steps based on a photodevelopment method. Furthermore, by completing the polymerization or curing process with heat (sometimes both are combined and referred to as curing), a light-shielding film with the desired pattern can be obtained.

[0120] As described above, the photosensitive resin composition for black resist of the present invention is not only suitable for forming fine patterns through exposure, alkaline development and other operations, but also can obtain a light-shielding film with excellent light-shielding, adhesion, electrical insulation, heat resistance and chemical resistance even when the pattern is formed by existing screen printing.

[0121] The photosensitive resin composition for black resist of the present invention is preferably used as a coating material. In particular, it is effectively used as a color filter ink for use in liquid crystal display devices or photographic elements, and as a light-shielding film formed from the ink, for use in color filters, black matrices for liquid crystal projectors, etc. Furthermore, in addition to being used as a color filter ink for color liquid crystal displays, the photosensitive resin composition for black resist of the present invention can also be used as an ink material for color division or light shielding in various multicolor displays such as organic electric field light-emitting devices represented by organic electroluminescence (EL) elements, color liquid crystal display devices, color fax machines, and image sensors. With the color filter of the present invention, the reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, or, for example, the reflection of light emitted from the element when used in organic EL elements, can be reduced. That is, the contrast of bright areas can be improved by reducing the reflection of external light, or the luminous efficiency can be improved by improving the light extraction efficiency from the light-emitting side. [Example]

[0122] Hereinafter, embodiments and comparative examples of the present invention will be specifically described, but the present invention is not limited to these. Furthermore, in the present invention, when the first decimal place is 0, the description below the decimal point is sometimes omitted regarding the content of each component.

[0123] The evaluation of the resins in the following synthesis examples, the evaluation of the average particle diameter and refractive index of the inorganic particles, and the calculation of the RED values ​​between the components are performed as follows, unless otherwise specified.

[0124] [Solid component concentration] The weight of 1 g of the resin solution obtained in the synthesis example after being immersed in a glass filter [weight: W0(g)] and weighed [W1(g)], and the weight of the solution after being heated at 160°C for 2 hours [W2(g)], is calculated according to the following formula. Solid component concentration (wt%) = 100 × (W₂ - W₀) / (W₁ - W₀)

[0125] [Acid Value] The resin solution was dissolved in dioxane, and the solution was determined by titration using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) and a 1 / 10 N-KOH aqueous solution.

[0126] [Molecular weight] The weight-average molecular weight (Mw) was determined using a gel permeation chromatography (GPC) system (HLC-8220GPC, manufactured by Tosoh Corporation; solvent: tetrahydrofuran; columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation); temperature: 40°C; speed: 0.6 ml / min). The values ​​were converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) to determine the molecular weight.

[0127] [Average Particle Diameter] The average particle diameter of the inorganic particles was determined using a particle size analyzer, the FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), employing the dynamic light scattering method and the cumulative method.

[0128] [Calculation of RED value] Dispersions of components (A), (D), (E), and (F) were each added to a sample vial at a rate of 0.05 g (solid concentration: 100%). 5 mL of the specified pure solvent was added, and the mixture was stirred at room temperature (20°C) for 30 minutes. The stirred mixture was allowed to stand for 1 hour and visually observed. If no impurities were observed to precipitate, the solvent was considered a good solvent relative to the component; if impurities were observed to precipitate, the solvent was considered a poor solvent relative to the component. Furthermore, for the dispersion of component (D), after standing for 1 hour, the sample vial was inverted, and the state one minute after inversion was used to determine whether impurities were observed to precipitate.

[0129] The 24 solvents shown in Table 1 were used as the pure solvents.

[0130] [Table 1] No. solvent 1 acetone 2 Diacetone alcohol (DAA) 3 ethanol 4 γ-Butyrolactone 5 N-Methylpyrrolidone 6 Propylene glycol monomethyl ether (MMPG) 7 Propylene glycol monomethyl ether acetate (PGMEA) 8 Propylene glycol diacetate (PGDA) 9 Toluene 10 1-Butanol 11 2-Phenoxyethanol 12 Cyclohexanol 13 diethylene glycol 14 dimethylformamide 15 dimethyl sulfoxide 16 dipropylene glycol 17 Methyl isobutyl ketone (4-methyl-2-pentanone) 18 Dichloromethane 19 Butyl acetate (n-butyl acetate) 20 Propylene carbonate (4-methyl-1,3-dioxacyclopentan-2-one) twenty one Tetrachloroethylene twenty two methanol twenty three Acetonitrile twenty four hexane

[0131] To determine whether the 24 solvents are good or bad solvents for each component, the score for good solvents is set to 1, and the score for bad solvents is set to 0. Using HSPP as the HSP determination program, the HSP (dispersion force term δD, dipole interaction term δP, hydrogen bond term δH) of each component is calculated. For component (F), the interaction radius R0 is also calculated.

[0132] Furthermore, the distance Ra between the HSPs of components (A), (D), and (E) and component (F) is calculated using the following formula. In the following formula, the coordinate values ​​of the dispersions of components (A), (D), and (E) in Hansen space are set as (δDx, δPx, δHx), and the coordinate values ​​of component (F) in Hansen space are set as (δDy, δPy, δHy).

[0133] [Formula 2]

[0134] The RED value is calculated by dividing the distance Ra between the HSPs by the interaction radius R0 (Ra / R0) with respect to the (F) component.

[0135] First, an alkali-soluble resin containing unsaturated groups, which is component (A), is synthesized by the following method.

[0136] The abbreviations used in the synthesis examples are as follows. BPFE: Bisphenol A type epoxy compound (the reaction product of 9,9-bis(4-hydroxyphenyl) epoxide and chloromethyloxetane. In compounds of general formula (1), X is epoxide-9,9-diyl and R1~R4 are hydrogen compounds). AA: Acrylic acid BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0137] [Synthesis Example A1] A 500 ml four-necked flask equipped with a reflux condenser was loaded with BPFE (50.0 g, 0.10 mol), AA (14.1 g, 0.20 mol), PGMEA (67 g), and TPP (0.26 g), and stirred at 100°C–105°C for 12 hours to carry out the reaction. Subsequently, BPDA (14.4 g, 0.05 mol) and THPA (7.4 g, 0.05 mol) were loaded into the flask, and stirred at 120°C–125°C for 6 hours to obtain an unsaturated alkali-soluble resin (A)-1. The obtained resin solution had a solids concentration of 56% by mass, an acid value (converted from solids content) of 96 mg KOH / g, and a Mw of 3600 obtained by GPC analysis.

[0138] [Synthesis Example A2] A 500 ml four-necked flask equipped with a reflux condenser was loaded with BPFE (50.0 g, 0.1 mol), AA (14.1 g, 0.20 mol), PGMEA (67 g), and TPP (0.26 g), and stirred at 100°C–105°C for 12 hours to carry out the reaction. Subsequently, BPDA (10.1 g, 0.03 mol) and THPA (11.9 g, 0.08 mol) were loaded into the flask, and stirred at 120°C–125°C for 6 hours to obtain an unsaturated alkali-soluble resin (A)-2. The obtained resin solution had a solids concentration of 56% by mass, an acid value (converted from solids content) of 98 mg KOH / g, and a Mw of 2300 obtained by GPC analysis.

[0139] [Synthesis Example A3] A 500 ml four-necked flask equipped with a reflux condenser was loaded with BPFE (50.0 g, 0.1 mol), AA (14.1 g, 0.20 mol), PGMEA (67 g), and TPP (0.26 g), and stirred at 100°C–105°C for 12 hours to carry out the reaction. Subsequently, BPDA (20.9 g, 0.07 mol) and THPA (0.23 g, 0.015 mol) were loaded into the flask, and stirred at 120°C–125°C for 6 hours to obtain an unsaturated alkali-soluble resin (A)-3. The obtained resin solution had a solids concentration of 56% by mass, an acid value (converted from solids content) of 102 mg KOH / g, and a Mw of 7000 obtained by GPC analysis.

[0140] [Synthesis Example A4] In a 1000 ml four-necked flask equipped with a nitrogen inlet and reflux tube, 51.7 g (0.60 mol) of MAA, 38.4 g (0.38 mol) of MMA, 36.3 g (0.22 mol) of CHMA, 5.9 g of AIBN, and 320 g of DMDG were charged and polymerized by stirring under a nitrogen stream at 80-85°C for 8 hours. Then, 39.2 g (0.28 mol) of GMA, 1.4 g of TPP, and 0.06 g of DTBC were charged into the flask, and the mixture was stirred at 80-85°C for 16 hours to obtain an alkali-soluble resin (A)-4 containing polymerizable unsaturated groups. The obtained resin solution had a solids concentration of 35% by mass, an acid value (converted from solids content) of 110 mgKOH / g, and a weight-average molecular weight (Mw) of 18000 obtained by GPC analysis.

[0141] In addition, carbon black with a surface coated with dye was prepared by the following method.

[0142] [Preparation Example D1] 1000 g of carbon black (TPX-1099: manufactured by Cabot Corporation) was mixed with water to prepare 10 L of slurry. The mixture was stirred at 95°C for 1 hour and then cooled before washing with water. This was repeated to prepare another 10 L of slurry, with 42.9 g of 70% nitric acid added and stirred at 40°C for 4 hours. After cooling and washing with water, the mixture was again mixed to prepare another 10 L of slurry, with 769.2 g of 13% sodium hypochlorite aqueous solution added and stirred at 40°C for 6 hours. After cooling and washing with water, the mixture was again mixed to prepare another 10 L of slurry, with 38.1 g of 38.4% pure dye (Direct Deep Black) added and stirred at 40°C for 1 hour. Then, 10.1 g of aluminum sulfate was added and stirred at 40°C for 1 hour. After cooling, the mixture was washed with water, filtered, and dried to obtain dye-coated carbon black.

[0143] The dye-coated carbon black, polymeric dispersant, and PGMEA are mixed and dispersed using a bead mill to obtain a carbon black dispersion (D)-1 with a dye-coated carbon black concentration of 25.0% by mass and a polymeric dispersant concentration of 10.0% by mass.

[0144] The photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 2 were prepared using the formulation amounts (in parts by mass) listed in Table 2. The formulation components used in Table 2 are described below. Furthermore, the values ​​listed in Table 2 as the amounts of components (D) and (E) are the formulation amounts of a dispersion containing dispersants, etc.

[0145] (Alkali-soluble resins containing unsaturated groups) (A)-1: The alkali-soluble resin solution containing unsaturated groups obtained in Synthesis Example A1 (solid content concentration of 56.0% by mass). (A)-2: The alkali-soluble resin solution containing unsaturated groups obtained in Synthesis Example A2 (solid content concentration of 56.0% by mass). (A)-3: The alkali-soluble resin solution containing unsaturated groups obtained in Synthesis Example A3 (solid content concentration of 56.0% by mass). (A)-4: The alkali-soluble resin solution containing unsaturated groups obtained in Synthesis Example A4 (solid content concentration of 56.0% by mass).

[0146] (Photopolymerizable compounds) (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Dong-A Synthetic Co., Ltd., "Aronix" is a registered trademark of the company).

[0147] (Photopolymerization initiator) (C): Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-chloro-3-yl]-,1-(O-acetylgoxime) (Irgacure OXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of the company)

[0148] (Dispersion of the light-blocking component) (D)-1: Preparation of dye-coated carbon black obtained in Example D1. A pigment dispersion (35% by mass) of PGMEA solvent with a concentration of 25% by mass and a polymeric dispersant concentration of 10% by mass. (D)-2: Uncoated carbon black. Pigment dispersion (38% by weight) of PGMEA solvent with a concentration of 25% by weight and a polymeric dispersant concentration of 13% by weight.

[0149] (A dispersion of inorganic particles) (E)-1: A silica dispersion (solids content 25% by mass) consisting of 20% by mass silica particles with an average particle size of 76 nm and 5% by mass PGMEA solvent as a polymeric dispersant. (E)-2: A silica dispersion (solids content 26% by mass) consisting of 20% by mass silica particles with an average particle size of 71 nm and 6% by mass PGMEA solvent as a polymeric dispersant. (E)-3: PGMEA dispersion of silicon dioxide particles "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration of 30% by mass, average particle size of 50 nm) (E)-4: PGMEA dispersion of silicon dioxide particles "SIRPMA-H98" (manufactured by CIK Nanotechnology Co., Ltd., solid content concentration of 25% by mass, average particle size of 125 nm) (E)-5: Alumina dispersion (alumina dispersion of 10% by mass alumina particles and 5% by mass PGMEA solvent as polymeric dispersant) (solid content 15% by mass, average particle size 50 nm) (E)-6: Magnesium fluoride dispersion (MgF2 20% by mass, polymeric dispersant 6% by mass (solid content 26% by mass), average particle size 47 nm)

[0150] (Dispersant) (F)-1: Disperbyk-167 (solid content concentration of 52% by mass) (F)-2: Disperbyk-9076 (solid content concentration 100% by mass) Furthermore, (F)-1 to (F)-2 are all manufactured by BYK-Chemie Japan, and "DISPERBYK" is a registered trademark of the company.

[0151] In addition, (F)-1 is a carbamate-based dispersant, and (F)-2 is a dispersant with an alkylammonium salt structure of a polymer copolymer having an acid group.

[0152] (solvent) (G)-1: Propylene glycol monomethyl ether acetate (PGMEA) (G)-2: Cyclohexanone (ANON)

[0153] [Table 2] Blending ingredients Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 1 2 (A)Ingredients (A)-1 5.1 5.1 5.3 5.3 5.1 5.1 5.3 5.3 5.0 5.2 4.0 (A)-2 5.1 (A)-3 5.1 (A)-4 8.2 (B) Ingredients (B) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.5 1.6 (C) Components (C) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (D) Components (D)-1 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 24.2 (D)-2 24.2 (E) Components (E)-1 2.63 2.63 2.63 2.63 2.63 2.63 (E)-2 2.63 2.63 (E)-3 1.75 1.75 (E)-4 2.11 2.11 (E)-5 5.3 (E)-6 2.6 (F)Ingredients (F)-1 0.11 0.11 0.11 0.11 (F)-2 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 (G) component (G)-1 27.3 27.3 27.9 27.6 27.3 27.4 28 27.6 27.3 27.3 23.3 25.7 28.5 24.2 (G)-2 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7

[0154] [evaluate] The following describes the preparation of a light-shielding film for evaluation, which is made by curing a black photoresist with a photosensitive resin composition.

[0155] (The fabrication of the light-shielding film used for evaluation) Using a spin coater, the photosensitive resin composition shown in Table 1 was coated onto a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate") that had been pre-cleaned by irradiating a 254 nm wavelength ultraviolet light with an illuminance of 1000 mJ / cm² with a low-pressure mercury lamp. A light-shielding film was then pre-baked at 90°C for 1 minute using a hot plate to create a light-shielding film. Subsequently, the exposure gap was adjusted to 100 μm, and a negative photoresist with a line / space ratio of 10 μm / 50 μm was coated onto the dried light-shielding film. The photosensitive portion was then irradiated with 50 mJ / cm² ultraviolet light using an ultra-high-pressure mercury lamp with an illuminance of 30 mW / cm² to induce a photocuring reaction.

[0156] Subsequently, the exposed light-shielding film was subjected to development treatment at 25°C using a 0.04% potassium hydroxide solution at a spray pressure of 1 kgf / cm² for 10 seconds and 20 seconds from the time the pattern began to appear (break time = BT). Then, it was sprayed with water at 5 kgf / cm² to remove the unexposed portion of the light-shielding film and form a light-shielding film pattern on a glass substrate. It was then formally cured (post-baked) at 230°C using a hot air dryer for 30 minutes to obtain the light-shielding films used for evaluation in Examples 1 to 10 and Comparative Examples 1 to 2.

[0157] Regarding the light-shielding film used for the evaluation, the following items are evaluated.

[0158] [Optical density (OD) evaluation] (Evaluation Method) Optical density (OD) was measured using a transilluminance meter (X-rite 361T(V) manufactured by X-rite Corporation). The optical density (OD) per 1 μm of film thickness was calculated based on the measured film thickness and optical density (OD).

[0159] Optical density (OD) is calculated using the following equation (7). Optical density (OD) = -log 10T Equation (7) (T represents transmittance)

[0160] [Evaluation of Pattern Linearity] (Evaluation Method) For the 10 μm mask pattern after formal curing (post-baking), the rough edges of the pattern were observed using an optical microscope and a scanning electron microscope (SEM). Furthermore, the straightness of the pattern was evaluated under BT+10 seconds and BT+20 seconds conditions. Additionally, a value of ○ or higher was considered acceptable.

[0161] (Evaluation Criteria) ◎: No rough edges were found on the sides of the pattern. ○: In some areas, rough edges were found on one side of the pattern. △: Rough edges were found on both sides of the pattern in some areas. ×: Overall, rough edges were found on both sides of the pattern.

[0162] [Reflectivity Evaluation] (Evaluation Method) For a substrate with a light-shielding film manufactured in the same manner as the light-shielding film used for evaluation, the reflectance of the substrate (glass substrate) side was measured using a UV-Vis infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) at an incident angle of 2°. Furthermore, a reflectance of less than 6.0% was considered acceptable.

[0163] [Evaluation of Condensed Foreign Matter] (Evaluation Method) The light-shielding film used for evaluation after formal hardening (post-baking) was observed using an optical microscope to confirm the presence or absence of condensed foreign matter. Furthermore, a value of △ or higher was considered acceptable.

[0164] (Evaluation Criteria) ◎: No condensed foreign matter was detected on the light-shielding film. ○: Condensed foreign matter was found in a portion of the light-shielding film, but could not be confirmed visually. △: Condensed foreign matter that could be visually identified was found in a portion of the light-shielding film. ×: Condensed foreign matter that could be visually identified was found across the entire surface of the light-shielding film.

[0165] [Overall Evaluation] Based on the evaluation results of pattern linearity, reflectivity, and foreign matter, a comprehensive evaluation of each photosensitive resin component was conducted. ◎: Reflectivity is less than 6.0%, and the evaluation results for pattern linearity and foreign objects are both ◎. ○: Reflectivity less than 6.0%, and no evaluation results for pattern linearity and foreign objects. △ △: Reflectivity is less than 6.0%, and at least one of the evaluation results for pattern linearity and foreign matter is △ ×: There are unqualified evaluation items.

[0166] The evaluation results are shown in Table 3.

[0167] [Table 3] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 1 2 RED value (A)(F) Inter-component 0.89 0.89 0.89 0.89 0.77 0.77 0.77 0.77 0.69 0.76 0.89 0.89 0.76 1.13 (E)(F) Inter-component 0.82 0.56 1.97 1.4 0.47 0.7 1.46 1.2 0.47 0.47 0.90 0.51 0.47 0.56 (D)(F) Intercomponents 0.51 0.51 0.51 0.51 0.34 0.34 0.34 0.34 0.34 0.34 0.51 0.51 0.53 0.51 OD ( / μm) 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 linearity of the pattern ○ △ △ ◎ ◎ ○ ○ ◎ ◎ ◎ ○ ○ △ × reflectivity 5.0 5.0 4.8 5.3 4.8 5.0 4.8 5.2 4.8 4.8 5.0 5.2 6.8 5.0 foreign body ○ △ △ △ ◎ ○ ○ ○ ◎ ◎ ○ ○ ○ × Comprehensive evaluation of characteristics ○ △ △ △ ◎ ○ ○ ○ ◎ ◎ ○ ○ × ×

[0168] (Inspection) As can be seen from Tables 2 and 3, a photosensitive resin composition that meets the following conditions through the dispersion of component (A) (photosensitive resin containing unsaturated groups), component (D) (light-blocking component), component (E) (inorganic particles), and component (F) (dispersant) can form a highly fine pattern, can sufficiently reduce reflectivity, and can suppress the generation of aggregated foreign matter. The RED value between component (A) and component (F) is less than 1.00 MPa 1 / 2. The RED value between the dispersion of component (D) and component (F) is less than 0.51 MPa 1 / 2. The RED value between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2.

[0169] Furthermore, it is known that the optimal RED value varies depending on the component. For example, if the RED value between component (A) and component (F) is less than 1.00 MPa 1 / 2, good results can be obtained. However, if the RED value between the dispersion of component (D) and component (F) is not set to less than 0.51 MPa 1 / 2, good results cannot be obtained. [Industry availability]

[0170] The photosensitive resin composition of the present invention provides a photosensitive resin composition for a black matrix that balances high light-blocking properties and low reflectivity, as well as a light-blocking film using the photosensitive resin composition for a black matrix, a color filter, and a touch panel. Furthermore, the color filter and touch panel provide various display devices with excellent visibility.

Claims

1. A photosensitive resin composition for a black photoresist, comprising: (A) Photosensitive resin containing unsaturated groups; (B) Photopolymerizable compounds having at least two or more unsaturated bonds; (C) Photopolymerization initiator; (D) At least one light-shielding component selected from the group consisting of black pigments, mixed pigments, and light-shielding materials; (E) Inorganic particles with a refractive index of 1.10 or higher and 1.80 or lower; and (F) Dispersant. Regarding components (A), (D), (E), and (F), when the radius of Hansen's dissolution sphere, i.e., the interaction radius of component (F), is set as R0, and the distance between the Hansen solubility parameter of each component or dispersion and the Hansen solubility parameter of component (F) is set as Ra, the relative energy difference between each component or dispersion and component (F), represented by Ra / R0, satisfies the following conditions: the relative energy difference between component (A) and component (F) is 1.00 MPa1 / 2 or less; the relative energy difference between the dispersion of component (D) and component (F) is 0.51 MPa1 / 2 or less. The relative energy difference between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2.

2. The photosensitive resin composition for black resist as claimed in claim 1, wherein the (A) photosensitive resin containing unsaturated groups is a photosensitive resin containing unsaturated groups obtained by reacting an epoxy compound with two glycidyl ether groups derived from bisphenols, represented by the following general formula (1), with the reaction product of (meth)acrylic acid, and then with a polycarboxylic acid or its anhydride, wherein in formula (1), R1, R2, R3 and R4 are each independently any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fucoid-9,9-dimethyl or single bond represented by general formula (2), and l is an integer from 0 to 10.

3. The photosensitive resin composition for black resist as claimed in claim 1 or 2, wherein the relative energy difference between the dispersion of said component (D) and said component (F) is less than 0.40 MPa 1 / 2.

4. The photosensitive resin composition for black resist as claimed in claim 1 or 2, wherein the Hansen solubility parameter-relative energy difference between the dispersion of said component (E) and said component (F) is less than 0.85 MPa 1 / 2.

5. The photosensitive resin composition for black resist as claimed in claim 1 or 2, wherein the Hansen solubility parameter-relative energy difference between the dispersion of said component (E) and said component (F) is greater than 0.85 MPa 1 / 2 and less than 2.00 MPa 1 / 2.

6. The black photosensitive resin composition for resist as claimed in claim 1 or 2, wherein the dispersion of said component (E) comprises a dispersant.

7. The photosensitive resin composition for black resist as claimed in claim 1 or 2, wherein the (E) component is an inorganic particle selected from the group consisting of silicon dioxide particles, aluminum oxide particles, and magnesium fluoride particles.

8. A method for manufacturing a photosensitive resin composition for a black photoresist, comprising: (A) a photosensitive resin containing unsaturated groups; (B) a photopolymerizable compound having at least two or more unsaturated bonds; (C) a photopolymerization initiator; (D) a dispersion of at least one opaque component selected from the group consisting of black pigment, mixed pigment, and opaque material, dispersed in a solvent; (E) an inorganic particle dispersion dispersed in a solvent; and (F) a dispersant, wherein, regarding the dispersions of components (A), (D), (E), and (F), the dispersions of components (A), (D), (E), and (F) are selected as follows: when the radius of the Hansen solubility sphere, i.e., the interaction radius of component (F), is set to R0, and the distance between the Hansen solubility parameter of each component or dispersion and the Hansen solubility parameter of component (F) is set to Ra, Ra / R The relative energy difference between each component or dispersion and component (F), represented by 0, satisfies the following conditions: the relative energy difference between component (A) and component (F) is less than 1.00 MPa 1 / 2; the relative energy difference between the dispersion of component (D) and component (F) is less than 0.51 MPa 1 / 2; and the relative energy difference between the dispersion of component (E) and component (F) is less than 2.00 MPa 1 / 2.

9. A method for manufacturing a photosensitive resin composition for a black resist as described in claim 8, wherein the dispersion of said component (E) comprises a dispersant.

10. A method for manufacturing a photosensitive resin composition for a black resist as claimed in claim 8 or 9, wherein the dispersion of the (E) component is a dispersion of inorganic particles selected from the group consisting of alumina particles and magnesium fluoride particles.

11. A light-shielding film, which is formed by curing a black resist as described in claim 1 or 2 with a photosensitive resin composition.

12. A color filter having a light-shielding film as described in claim 11 as a black matrix.

13. A touch panel having a light-shielding film as described in claim 11.

14. A display device having a color filter as described in claim 12.

15. A display device having a touch panel as described in claim 13.