Method for manufacturing substrate with light-shielding film

Abstract

To provide a method for manufacturing a substrate with a light-shielding film which suppresses reflectance of both of a surface on a transparent substrate side of a light-shielding film and a surface opposite to the surface.SOLUTION: A method for manufacturing a substrate with a light-shielding film includes a step of forming a resin composition layer for antireflection on a transparent substrate, a step of forming a resin composition layer for a light-shielding layer containing a light-shielding component (D), a photopolymerization initiator (E) and an alkali-soluble resin (B) thereon, and a step of collectively performing exposure treatment, development treatment and thermal curing treatment on the layers, and forming a light-shielding film composed of an antireflection layer and a light-shielding layer, wherein the resin composition layer for antireflection has (1) to (3): (1) an inorganic filler (A) having a refractive index of 1.2 to 1.8 and an average particle diameter of 10 nm or more and less than 125 nm, and an alkali-soluble resin (B), and 10 to 80 mass% of (A) in a solid content; (2) average thickness of 0.01 to 0.4 μm; and (3) a residual film rate of 10 to 90% when the resin composition layer for antireflection having average thickness of 1.2 μm is immersed in PGMEA for 5 seconds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a substrate with a light-shielding film. [Background technology]

[0002] In recent years, with the development of mobile terminals, there has been an increase in display devices having touch panels or liquid crystal panels for use outdoors or in vehicles. In 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 black is displayed and to suppress color mixing between adjacent color resists. Known light-shielding films are formed on transparent substrates using photosensitive resin compositions containing light-shielding components such as black pigments. However, in display devices having a transparent substrate on the surface of which a light-shielding film is disposed, light incident from the transparent substrate side is reflected by the surface of the light-shielding film (at the interface with the transparent substrate), causing a problem of surrounding objects being reflected on the screen.

[0003] In order to solve the problem of such reflections, attempts have been made to achieve low reflection from the transparent substrate side by forming, for example, a multilayer film of two or more layers as an optical interference film on the transparent substrate.

[0004] For example, Patent Document 1 describes that in a display panel substrate having a transparent substrate and a light-shielding layer, two types of light-shielding layers with different optical densities are provided on the transparent substrate as light-shielding layers, and a light-shielding layer with a lower optical density than the light-shielding layer with a higher optical density is disposed between the transparent substrate and the light-shielding layer with a higher optical density, thereby suppressing light reflection on the surface of the light-shielding layer.

[0005] Furthermore, Patent Document 2 describes that in a display device substrate having a transparent substrate and a black matrix, reflection of light on the surface of the black matrix is ​​suppressed by laminating a reflectance-reducing layer and a light-shielding layer on the transparent substrate, the effective optical density of which is within a specific range as a black matrix.

[0006] Patent document 3 also describes a color filter and liquid crystal display device having a light-blocking material on a transparent support, in which the light-blocking material has a specific optical density and is composed of two or more layers, the first layer in contact with the support containing silica and / or resin particles, and the color filter and liquid crystal display device have the characteristics of having a low relative reflectance of a specific wavelength for light incident from the transparent support (transparent glass substrate) side.

[0007] Furthermore, Patent Document 4 describes that in a substrate with a light-shielding material having a light-shielding material on a transparent substrate, productivity and low reflectivity can be achieved by, for example, containing silica microparticles in the light-shielding material and varying the concentration of the microparticles in the thickness direction.

[0008] Furthermore, Patent Document 5 describes that in a substrate for a display device comprising a transparent substrate and a light-shielding film, by providing a light-shielding film on the transparent substrate, which comprises an anti-reflection layer and a light-shielding layer as a light-shielding film, and in which the surface roughness of the anti-reflection layer at the interface between the anti-reflection layer and the light-shielding layer is within a specific range, reflection of light on the surface of the light-shielding film can be effectively suppressed.

[0009] Furthermore, Patent Document 6 describes that in an information display device having a cured film for information display devices, which includes a colored cured film and a transparent cured film, formed on a support such as glass, high light blocking and low reflectance can be simultaneously achieved by adjusting the optical density, refractive index, and film thickness of the colored cured film and the film thickness and refractive index of the transparent cured film within predetermined ranges. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] International Publication No. 2010 / 070929 [Patent Document 2] International Publication No. 2014 / 178149 [Patent Document 3] Patent No. 6241153 [Patent Document 4] Patent No. 6354840 [Patent Document 5] Japanese Patent Publication No. 2020-098334 [Patent Document 6] Japanese Patent Application Publication No. 2023-024297 Summary of the Invention [Problem to be solved by the invention]

[0011] However, while such conventional techniques can suppress light reflection and the above-mentioned glare at the interface on the transparent substrate (support) side, studies by the inventors of the present application have revealed that there is a problem of reducing the reflectance on the light-shielding film surface on the opposite side. That is, there was concern that external light reflection, such as light incident from the transparent substrate (support) side being reflected at the interface between the transparent substrate (support) and the light-shielding layer, or light reflected by the internal wiring of the device being reflected on the light-shielding layer surface on the opposite side from the transparent substrate (support) side, could cause problems such as reduced visibility. Therefore, it was found that suppressing the reflectance on both sides of the light-shielding layer, i.e., on both the transparent substrate side and the opposite side of the light-shielding layer, became a new challenge. In this regard, in order to suppress the reflectance on the surface opposite to the light-shielding layer, for example, a method of incorporating an inorganic filler such as silica fine particles into the light-shielding layer can be mentioned. However, it has been confirmed that incorporating such an inorganic filler may require adjustment of compatibility or may be prone to aggregation depending on the type and amount of the light-shielding component (e.g., carbon black) in the light-shielding layer, and therefore the stability of the light-shielding film may be insufficient. There is also concern that this may be a hindrance to achieving both high light-shielding and low reflectance, particularly when high light-shielding is desired.

[0012] The present invention has been made in consideration of such problems, and aims to provide a method for producing a substrate with a light-shielding film, which is stable and has reduced reflectance on both the surface facing the transparent substrate and the opposite surface when formed as a light-shielding film, without requiring the inclusion of inorganic fillers such as silica microparticles in the formation of the light-shielding layer. [Means for solving the problem]

[0013] That is, the gist of the present invention is as follows. [1] A method for producing a substrate with a light-shielding film, which comprises a transparent substrate and a light-shielding film composed of an antireflection layer and a light-shielding layer, forming a resin composition layer for an antireflection layer on a transparent substrate; forming a resin composition layer for a light-shielding layer, which contains a light-shielding component (D), a photopolymerization initiator (E), and an alkali-soluble resin (B), on the resin composition layer for an antireflection layer; and a step of simultaneously subjecting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer to an exposure treatment, then simultaneously subjecting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer to a development treatment, and further subjecting the resin composition layer for an antireflection layer and the light-shielding layer to a heat-curing treatment, thereby forming a light-shielding film comprising an antireflection layer and a light-shielding layer, A method for producing a substrate with a light-shielding film, characterized in that the resin composition layer for an antireflection layer satisfies the following (1) to (3): (1) The composition contains an inorganic filler (A) having a refractive index of 1.2 to 1.8 and an average particle size of 10 nm or more and less than 125 nm, and an alkali-soluble resin (B), and the inorganic filler (A) is contained in an amount of 10 to 80 mass % in the solid content. (2) The average thickness is 0.01 to 0.4 μm. (3) When a film having an average thickness of 1.2 μm is immersed in propylene glycol monomethyl ether acetate for 5 seconds, the remaining film rate is 10 to 90%. [2] The method for producing a substrate with a light-shielding film according to [1], characterized in that the light-shielding layer contains at least one light-shielding component (D) selected from the group consisting of organic black pigments, inorganic black pigments, and mixed-color pseudo-black pigments, and an alkali-soluble resin (B), and has an average thickness of 0.1 to 30 μm. [3] The method for producing a substrate with a light-shielding film according to [1], wherein the resin composition layer for an antireflection layer contains a photopolymerizable monomer and / or an epoxy compound (C). [4] The method for producing a substrate with a light-shielding film according to [1], wherein the inorganic filler (A) has an average particle size of 30 nm or more and less than 125 nm. [5] The method for producing a substrate with a light-shielding film according to [1], wherein the resin composition layer for an antireflection layer has an average thickness of 0.01 to 0.2 μm. [6] The method for producing a substrate with a light-shielding film according to [1], wherein the inorganic filler (A) is contained in an amount of 30 to 80 mass % of the solid content. [7] The method for producing a substrate with a light-shielding film according to [1], wherein the alkali-soluble resin is an alkali-soluble resin containing an unsaturated group represented by the following general formula (II): [ka] [In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; X represents a tetravalent carboxylic acid residue; Y1 and Y2 each independently represent a hydrogen atom or -OC-Z-(COOH)m (wherein Z represents a divalent or trivalent carboxylic acid residue and m is a number from 1 to 2); and n represents an integer from 1 to 20.] [Effects of the Invention]

[0014] According to the present invention, it is possible to produce a substrate with a light-shielding film that is stable and has reduced reflectance on both the surface facing the transparent substrate and the surface opposite to it when formed as a light-shielding film, without necessarily requiring the inclusion of an inorganic filler such as silica fine particles in the formation of the light-shielding layer. The substrate with a light-shielding film obtained by this method can be used for a black matrix used in a color filter or touch panel, or for a partition material or pixel-defining layer for each color separation or light blocking in various multicolor display devices such as electroluminescent devices typified by organic EL elements, color liquid crystal display devices, or image sensors, as well as display components such as a bezel surrounding the display area of ​​the display. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an embodiment of the present invention will be described.

[0016] The method for producing the substrate with a light-shielding film of the present invention will be described below. The method for producing a substrate with a light-shielding film of the present invention is a method for producing a substrate with a light-shielding film, which comprises a transparent substrate and a light-shielding film composed of an antireflection layer and a light-shielding layer, and includes the steps of: forming a resin composition layer for an antireflection layer on a transparent substrate; forming a resin composition layer for a light-shielding layer, which contains a light-shielding component (D), a photopolymerization initiator (E), and an alkali-soluble resin (B), on the resin composition layer for an antireflection layer; The method includes a step of simultaneously subjecting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer to an exposure treatment, then simultaneously subjecting them to a development treatment, and further subjecting them to a heat curing treatment to form a light-shielding film consisting of an antireflection layer and a light-shielding layer, wherein the resin composition layer for an antireflection layer is characterized by satisfying the following (1) to (3): (1) The composition contains an inorganic filler (A) having a refractive index of 1.2 to 1.8 and an average particle size of 10 nm or more and less than 125 nm, and an alkali-soluble resin (B), and the inorganic filler (A) is contained in an amount of 10 to 80 mass % in the solid content. (2) The average thickness is 0.01 to 0.4 μm. (3) When a film having an average thickness of 1.2 μm is immersed in propylene glycol monomethyl ether acetate for 5 seconds, the remaining film rate is 10 to 90%.

[0017] 1. Step of forming a resin composition layer for an antireflection layer The present invention first includes a step of forming a resin composition layer for an antireflection layer on a transparent substrate. The transparent substrate is not particularly limited, and examples thereof include glass substrates, transparent resin films (PET film, PEN film, polycarbonate film, polyimide film, etc.), and transparent substrates used in known display devices.

[0018] When forming the resin composition layer for an antireflection layer, a resin composition for an antireflection layer is used. As described in (1) above, the resin composition for an antireflection layer contains an inorganic filler (A) having a refractive index of 1.2 to 1.8 and an average particle size of 10 nm or more and less than 125 nm, and an alkali-soluble resin (B).

[0019] <Inorganic filler (A)> The inorganic filler (A) has a refractive index of 1.2 to 1.8. Preferably, the inorganic filler (A) having such a refractive index has a refractive index smaller than that of the light-shielding component (D) described below. Use of the inorganic filler (A) having such a refractive index is preferred because, when formed into a light-shielding film, the reflectance of the light-shielding film is reduced and light reflection on the light-shielding film is suppressed. The refractive index of the inorganic filler (A) is preferably 1.3 to 1.6, and more preferably 1.4 to 1.5.

[0020] The inorganic filler (A) having such a refractive index is not limited, and examples thereof include silica (refractive index: 1.46), magnesium fluoride (refractive index: 1.38), lithium fluoride (refractive index: 1.39), and calcium fluoride (refractive index: 1.40). Among these, silica (refractive index: 1.46) is particularly preferred. Furthermore, such inorganic filler (A) (particularly silica) is preferably manufactured or surface-treated so as to be dispersible in an organic solvent. Examples of silica manufactured or surface-treated so as to be dispersible in an organic solvent include fumed silica, colloidal silica, and organosilica sol. Examples of silica that can be dispersed in an organic solvent include those sold under the trade names Organosilica Sol manufactured by Nissan Chemical Industries, Ltd., Adma Fine and Admanano manufactured by Admatechs Co., Ltd., Colloidal silica, Organosilica Sol, and Silica Nanopowder manufactured by Fuso Chemical Co., Ltd., and Fumed Silica manufactured by Nippon Aerosil Co., Ltd.

[0021] The inorganic filler (A) has an average particle size of 10 nm or more and less than 125 nm. By using an inorganic filler (A) having such an average particle size, when formed into a light-shielding film, the reflectance of both the surface of the light-shielding layer facing the transparent substrate and the surface on the opposite side can be suppressed. Furthermore, the film remaining ratio (described below) can be set within a predetermined range. The inorganic filler (A) preferably has an average particle size of 30 nm or more and less than 125 nm, more preferably 30 nm or more and 100 nm or less, and even more preferably 30 to 80 nm. When the average particle size of the inorganic filler (A) is less than the lower limit, the reflectance of the light-shielding film tends to be high. On the other hand, when the average particle size exceeds the upper limit, the reflectance of the light-shielding film tends to be high and the film remaining ratio (described below) tends to be high. The average particle size of the inorganic filler (A) can be determined by particle size distribution measurement using a dynamic light scattering method or the like.

[0022] The content of the inorganic filler (A) is set to 10 to 80 mass% based on the solid content of the resin composition layer for an antireflection layer or the resin composition for an antireflection layer forming the same. The content of the inorganic filler (A) based on the solid content is preferably 20 to 80 mass%, more preferably 30 to 80 mass%. If the content of the inorganic filler (A) is less than the lower limit, the reflectance of the light-shielding film tends to increase and the residual film ratio (described below) tends to decrease. On the other hand, if the content exceeds the upper limit, the alkali-soluble resin (B) component tends to decrease, making it difficult to form a film on a transparent substrate (support).

[0023] The component (A) is usually dispersed in a solvent to form a light-shielding component dispersion, which is then mixed with other formulation components, and a dispersant may be added at this time. The dispersant may be any known compound used to disperse pigments (light-shielding components) (e.g., compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion promoters, etc.) and the like, without any particular limitation.

[0024] <Alkali-soluble resin (B)> The alkali-soluble resin (B) is preferably an unsaturated group-containing alkali-soluble resin that has an acid value sufficient to impart alkali developability and that has appropriate photocurability in combination with the photopolymerizable monomer in component (C) described below. Any known unsaturated group-containing alkali-soluble resin can be used without limitation, but the following resins are more preferred because they have high heat resistance and are capable of forming high-resolution patterns.

[0025] A first example of an unsaturated group-containing alkali-soluble resin that can be preferably used as the alkali-soluble resin (B) is an epoxy(meth)acrylate acid adduct obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid (meaning acrylic acid and / or methacrylic acid), and then reacting the resulting epoxy(meth)acrylate compound having hydroxy groups with (a) a dicarboxylic acid or tricarboxylic acid or its monoanhydride and / or (b) a tetracarboxylic acid or its dianhydride. Examples of compounds having two or more epoxy groups that can be used to produce the epoxy(meth)acrylate acid adduct include bisphenol-type epoxy compounds and novolac-type epoxy compounds. Specifically, preferred examples include bisphenol-type epoxy compounds represented by the following general formula (I):

[0026] [ka]

[0027] In general formula (I), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; l is an integer of 0 to 10. R1, R2, R3, and R4 are preferably hydrogen atoms, and A is preferably a fluorene-9,9-diyl group. Since l typically contains multiple values, its average value is 0 to 10 (not necessarily an integer), but the average value of l is preferably 0 to 3. Hereinafter, the general formula (I) will be described assuming l=0.

[0028] Bisphenol-type epoxy compounds are epoxy compounds having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds containing two or more bisphenol skeletons.

[0029] The bisphenols used in this reaction include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl) 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)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)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9, 9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Among these, bisphenols having a fluorene-9,9-diyl group are particularly preferred.

[0030] The (a) dicarboxylic or tricarboxylic acid monoanhydride to be reacted with the epoxy (meth)acrylate obtained by reacting such an epoxy compound with (meth)acrylic acid may be a chain hydrocarbon dicarboxylic or tricarboxylic acid monoanhydride, an alicyclic dicarboxylic or tricarboxylic acid monoanhydride, or an aromatic dicarboxylic or tricarboxylic acid monoanhydride. Examples of the chain hydrocarbon dicarboxylic or tricarboxylic acid monoanhydride include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid monoanhydrides, and may also be dicarboxylic or tricarboxylic acid monoanhydrides having any substituent introduced therein. Furthermore, examples of the acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, and may also include acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced. Furthermore, examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, and may also include acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0031] The (b) tetracarboxylic acid dianhydride to be reacted with the epoxy (meth)acrylate may be a dianhydride of a chain hydrocarbon tetracarboxylic acid, a dianhydride of an alicyclic tetracarboxylic acid, or a dianhydride of an aromatic tetracarboxylic acid. Examples of the dianhydride of a chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid, and may also include a dianhydride of a tetracarboxylic acid having an optional substituent introduced therein. Examples of the dianhydride of a alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, and may also include a dianhydride of a tetracarboxylic acid having an optional substituent introduced therein. Furthermore, examples of the acid dianhydride of an aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid, and further may be acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced.

[0032] The molar ratio (a) / (b) of (a) a dicarboxylic or tricarboxylic acid monoanhydride to (b) a tetracarboxylic acid dianhydride to be reacted with the 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. When the molar ratio (a) / (b) is within the above range, it is easy to obtain an optimum molecular weight for preparing a photosensitive resin composition having good photopatterning properties, and alkali solubility is not impaired, which is preferable.

[0033] The reaction of an epoxy compound with (meth)acrylic acid and the reaction of the resulting epoxy (meth)acrylate with a polybasic carboxylic acid or its acid anhydride are not particularly limited, and known methods can be employed. For example, they can be produced by methods described in JP-A-8-278629 and JP-A-2008-9401. First, a method for reacting an epoxy compound with (meth)acrylic acid includes adding an equimolar amount of (meth)acrylic acid to a solvent relative to the epoxy groups of the epoxy compound, and then heating and stirring the mixture at 90 to 120°C while blowing in air in the presence of a catalyst (e.g., triethylbenzylammonium chloride, 2,6-diisobutylphenol). Next, a method for reacting an acid anhydride with the hydroxyl groups of the epoxy acrylate compound, the reaction product, includes adding predetermined amounts of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride to a solvent, and then heating and stirring the mixture at 90 to 130°C in the presence of a catalyst (e.g., tetraethylammonium bromide, triphenylphosphine). The epoxy acrylate acid adduct obtained by this method has a skeleton of general formula (II).

[0034] [ka]

[0035] In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; X represents a tetravalent carboxylic acid residue; Y1 and Y2 each independently represent a hydrogen atom or -OC-Z-(COOH)m (wherein Z represents a divalent or trivalent carboxylic acid residue and m represents a number of 1 to 2); and n represents an integer of 1 to 20.

[0036] Next, a second example of an unsaturated group-containing alkali-soluble resin that can be preferably used as the alkali-soluble resin (B) is a copolymer of (meth)acrylic acid, (meth)acrylic acid esters, etc., and includes a resin having a (meth)acryloyl group and a carboxy group. Examples of the resin include an unsaturated group-containing alkali-soluble resin obtained by copolymerizing (meth)acrylic acid esters including glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymer include a copolymer disclosed in Japanese Patent Laid-Open No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and which has a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH / g; and an unsaturated group-containing alkali-soluble resin disclosed in Japanese Patent Laid-Open No. 2018-141968, which is a polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, and which includes units derived from (meth)acrylic acid ester compounds and units having a (meth)acryloyl group and a di- or tricarboxylic acid residue.

[0037] Furthermore, a third example of an unsaturated group-containing alkali-soluble resin that can be preferably used for the alkali-soluble resin (B) is a urethane compound obtained by reacting a polyol compound having an ethylenically unsaturated bond in the molecule as a first component, a diol compound having a carboxyl group in the molecule as a second component, and a diisocyanate compound as a third component. For examples of resins of this type, see JP 2017-76071 A.

[0038] The weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 10,000, and more preferably 3,000 to 8,000. If the weight-average molecular weight (Mw) is less than 2,000, the pattern adhesion during development cannot be maintained, and pattern peeling is likely to occur. If the weight-average molecular weight (Mw) exceeds 10,000, development residues and residual films in unexposed areas are likely to remain. Furthermore, the alkali-soluble resin (B) preferably has an acid value in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, alkaline development may not proceed smoothly or special development conditions, such as strong alkali, may be required. If the acid value exceeds 200 mgKOH / g, the alkaline developer may penetrate too quickly, making peeling development more likely.

[0039] The content of the alkali-soluble resin (B) in the resin composition for an antireflection layer that forms the resin composition layer for an antireflection layer is preferably 5 to 90 mass %, more preferably 8 to 80 mass %, and even more preferably 10 to 70 mass % of the solid content. The content of the alkali-soluble resin (B) can be adjusted together with the photopolymerizable monomer in the component (C) described below.

[0040] <Average thickness> The average thickness of the resin composition layer for an antireflection layer in the present invention is set to 0.01 to 0.4 μm. A preferred average thickness is 0.02 to 0.3 μm, and a more preferred average thickness is 0.03 to 0.2 μm. If the average thickness of the resin composition layer for an antireflection layer is less than the lower limit, defects tend to occur more easily during coating film formation. On the other hand, if the average thickness exceeds the upper limit, the thickness of the resin composition layer for an antireflection layer tends to be non-uniform, which can easily lead to unevenness and abnormal appearance. The average thickness of the resin composition for an antireflection layer can be determined by measuring the step between the surface of the resin composition layer for an antireflection layer and the surface of the transparent substrate using a stylus-type step profiler and averaging the measured steps.

[0041] <Remaining film rate> Furthermore, the resin composition layer for an antireflection layer in the present invention has an average thickness of 1.2 μm, and when immersed in propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate; PGMEA) for 5 seconds, the residual film ratio (hereinafter, sometimes simply referred to as "remaining film ratio") is set to 10 to 90%. The lower limit of the residual film ratio of the resin composition layer for an antireflection layer is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more, and even more preferably 50% or more. On the other hand, the upper limit of the residual film ratio of the resin composition layer for an antireflection layer is preferably 85% or less, more preferably 80% or less, and even more preferably 75% or less. The residual film ratio is calculated from the ratio of the average thickness before immersion in PGMEA to the average thickness after immersion, as shown in the following formula (*): Residual film rate (%) = 100 x (average thickness after immersion) / (average thickness before immersion) ...(*)

[0042] Here, in the above-mentioned method for measuring the residual film ratio, the reason for setting the average thickness to 1.2 μm is that if the average thickness is too small or too large, the difference in the measured residual film ratio tends to be difficult to clarify. Similarly, the reason for setting the immersion time in PGMEA to 5 seconds is to clarify the difference in the measured residual film ratio. Regarding the average thickness, the resin composition layer for an antireflection layer before immersion is dried by volatilizing the organic solvent through pre-baking, as described below. On the other hand, for the resin composition layer for an antireflection layer after immersion, the average thickness of the dried film is measured by drying the PGMEA used for immersion until the weight change is approximately 5% or less, using, for example, a vacuum dryer. The average thickness is measured using a method using a stylus-type step profiler, as described above. It is necessary that the resin composition layer for an antireflection layer to be measured be sufficiently immersed in PGMEA, and this may be performed on a resin composition layer for an antireflection layer with a transparent substrate. It is generally preferable to use PGMEA whose main component is 99.5% (by mass) or more.

[0043] In the present invention, forming the resin composition layer for an antireflection layer so as to have the above-mentioned film retention rate is particularly preferable because, when formed as a light-shielding film, it becomes possible to obtain a light-shielding film in which the reflectance is suppressed on both the surface on the transparent substrate side and the surface on the opposite side. Although the mechanism by which the above-mentioned effect is obtained by forming the resin composition layer for an antireflection layer so as to have the above-mentioned film retention rate is not necessarily clear, it is presumed to be due to the following reason. That is, it has been confirmed that when a resin composition layer for an antireflection layer having such a film retention rate is formed and then a resin composition layer for a light-shielding layer (described below) is formed on this layer, the resin composition layer for an antireflection layer is thought to partially dissolve and mix with the resin composition layer for a light-shielding layer thereon, and these layers are partially dissolved and mixed together near the interface to form the layer. During this process, it is presumed that the inorganic filler (A) in the resin composition layer for antireflection layer is partially transferred to the resin composition layer for light-shielding layer and unevenly distributed on both sides of the resin composition layer for light-shielding layer, thereby making it possible to suppress the reflectance on both sides of the surface of the light-shielding film facing the transparent substrate and the opposite surface when the light-shielding film is formed.

[0044] In the present invention, by adjusting the residual film rate of the resin composition layer for antireflection layer in this manner, it becomes possible to obtain a light-shielding film having reduced reflectance on both the surface facing the transparent substrate and the surface opposite thereto when formed as a light-shielding film, even if the resin composition layer for light-shielding layer described below or the light-shielding layer formed therefrom does not necessarily contain the inorganic filler (A). Therefore, it is possible to achieve reduced reflectance on both surfaces of the light-shielding film, while particularly achieving high light-shielding and layer stability for the light-shielding layer (resin composition layer for light-shielding layer) described below.

[0045] The above-mentioned residual film ratio of the resin composition layer for an antireflection layer is preferably maintained at least until the next resin composition layer for a light-shielding layer is formed. That is, even if there is a so-called delay time (sometimes referred to as waiting time, standby time, Q-Time, etc.), which is a certain period of time between the step of forming a resin composition layer for an antireflection layer on a transparent substrate and the step of forming the next resin composition layer for a light-shielding layer, it is a preferred method to maintain the resin composition layer for an antireflection layer so that it has the above-mentioned residual film ratio. Such a delay time may or may not be provided as long as the residual film ratio is maintained. However, if a delay time is provided, it is preferably maintained under conditions that do not change the residual film ratio of the resin composition layer for an antireflection layer. For example, it is more preferable to avoid treatments such as ultraviolet irradiation and heat treatments under excessive temperature or time conditions.

[0046] In the present invention, the resin composition layer for an antireflection layer can have such a remaining film ratio by, but not limited to, adjusting the contents of the inorganic filler (A) and the alkali-soluble resin (B) in the resin composition for an antireflection layer to obtain this, modifying the surface of the inorganic filler, adjusting the molecular weight of the alkali-soluble resin, or adjusting the ratio of hydrophilic groups / hydrophobic groups in the alkali-soluble resin.

[0047] Here, examples of methods for forming a resin composition layer for an antireflection layer include a method in which the resin composition for an antireflection layer is applied to the transparent substrate and then subjected to a heat treatment (pre-bake) to remove the organic solvent. In other words, the resin composition for an antireflection layer is preferably used in the form of a solution containing an organic solvent. This is preferable because it allows the formation of a uniform resin composition layer for an antireflection layer. Such an organic solvent is preferably blended in the resin composition for an antireflection layer so that its content is 80 to 99.9 mass %. In this case, it is more preferable that the resin composition for an antireflection layer is blended so that the viscosity, as measured with a B-type or E-type viscometer, is 1 to 4 mPa·sec.

[0048] The organic solvent used in the resin composition for the antireflection layer is not particularly limited, and known organic solvents can be used. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol. Examples of suitable organic solvents include glycol ethers such as ethanol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxypropionate, 3-ethoxypropionate, 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. These organic solvents may be used alone or in combination.

[0049] Examples of methods for applying the resin composition for an antireflection layer to the transparent substrate include known solution immersion methods and spraying methods, as well as methods using a roller coater, land coater, slit coater, spin coater, etc. The heating temperature and heating time in the pre-baking can be appropriately set depending on the type of organic solvent used, etc. For example, the heating temperature can be set to 60 to 110°C (set so as not to exceed the heat resistance temperature of the transparent substrate), and the heating time can be set to 1 to 3 minutes.

[0050] <Other Components of Resin Composition Layer for Antireflection Layer> The resin composition layer for an antireflection layer may contain other components in addition to those described above. For example, it is possible to adjust the sensitivity of the resin composition layer for an antireflection layer when photoprocessing the layer or to impart curability by heating. In order to adjust such properties, it is preferable to contain a component (C) consisting of a photopolymerizable monomer (C-1) and / or an epoxy compound (C-2).

[0051] [Photopolymerizable Monomer (C-1)] The photopolymerizable monomer (C-1) can serve to crosslink molecules of the unsaturated group-containing alkali-soluble resin, which is a preferred embodiment of the component (B). Examples of the photopolymerizable monomer (C-1) include (meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate; 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Examples of the polymerizable monomer include (meth)acrylic acid esters such as glycerol tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, polyhydric alcohols such as pentaerythritol and dipentaerythritol, vinyl benzyl ether compounds of polyhydric phenols such as phenol novolac, and addition polymers of divinyl compounds such as divinylbenzene. Further examples include dendritic polymers having a (meth)acroyl group. Examples of dendritic polymers having (meth)acroyl groups include known dendritic polymers obtained by adding a thiol group in a polyvalent mercapto compound to a portion of the carbon-carbon double bond in the (meth)acroyl group of a polyfunctional (meth)acrylate compound. The photopolymerizable monomer (C-1) can be one or more of these.

[0052] Since the photopolymerizable monomer (C-1) fulfills the above-mentioned role, it is more preferable to use one having two or more unsaturated bonds (e.g., ethylenically unsaturated bonds) in order to exert its function. In addition, the acrylic equivalent, which is the molecular weight of the monomer divided by the number of (meth)acryloyl groups in one molecule, is 50 to 300.

[0053] The amount of the photopolymerizable monomer (C-1) to be blended is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and even more preferably 0 to 30 parts by mass, per 100 parts by mass of the total of the alkali-soluble resin (B) and the photopolymerizable monomer (C-1).

[0054] [Photopolymerization initiator (E)] The anti-reflection layer resin composition layer may contain a photopolymerization initiator (E). The photopolymerization initiator (E) is not limited, but examples thereof include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyl dimethyl ketal; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4' -Benzophenones such as dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 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 Biimidazole compounds such as 2,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; halomethyldiazole 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; 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,Halomethyl-s-triazine compounds such as 6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-Dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol- 3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-Dione = 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-O-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, Ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), Ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetate O-Acyloxime compounds such as acetyl oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; 2-ethyl Anthraquinones such as 1,2-benzanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, and methoxybutyl-3- Mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,Examples of the photopolymerization initiator (E) include thiol compounds such as 3'-thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid. Among these, O-acyloxime compounds are preferred from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition. Two or more types of these photopolymerization initiators (E) can also be used. In the present invention, the photopolymerization initiator (E) is used to include a sensitizer.

[0055] Alternatively, compounds that do not function as photopolymerization initiators or sensitizers by themselves but can enhance their photopolymerization initiator or sensitizer capabilities when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine-based compounds that are effective when used in combination with benzophenone. Examples of the amine-based compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0056] The amount of the photopolymerization initiator (E) is preferably 0 to 30 parts by mass, more preferably 0 to 25 parts by mass, per 100 parts by mass of the total of the alkali-soluble resin (B) and the photopolymerizable monomer (C-1).

[0057] [Epoxy compound (C-2)] As the epoxy compound (C-2), known compounds can be used without limitation. For example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, hydrogenated bisphenols, Examples of epoxy compounds having a glycidyl group include phenol A diglycidyl ether (e.g., Rikaresin HBE-100, manufactured by New Japan Chemical Co., Ltd.), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175, manufactured by Huntsman), and bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 2,Examples of epoxy compounds include alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0058] In addition, known curing agents and curing accelerators for the epoxy compounds can also be used. Curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, and the like, which contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, and the like, which contribute to the curing of epoxy resins.

[0059] [Ingredients other than those listed above] In addition, various additives such as a dispersant, a polymerization initiator other than those described above, a chain transfer agent, a non-photosensitive resin, an antioxidant, a plasticizer, a filler, a coupling agent, a surfactant, and a dye may be used in the resin composition layer for an antireflection layer, as needed.

[0060] <Solid content> The resin composition for an antireflection layer that forms the resin composition layer for an antireflection layer contains the above-mentioned components, and the solid content excluding the organic solvent (solid content includes monomers that become solid after drying or curing) is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %.

[0061] 2. Step of forming a resin composition layer for a light-shielding layer As described above, after forming the resin composition layer for an antireflection layer on the transparent substrate, a resin composition layer for a light-shielding layer containing the light-shielding component (D) and the alkali-soluble resin (B) is formed on the resin composition layer for an antireflection layer.

[0062] <Alkali-soluble resin (B)> Here, the alkali-soluble resin (B) may be the same as that described above. The content of the alkali-soluble resin (B) in the resin composition for a light-shielding layer that forms the resin composition layer for a light-shielding layer is preferably 5 to 90 mass %, more preferably 8 to 80 mass %, and even more preferably 10 to 50 mass % of the solid content. The content of the alkali-soluble resin (B) in the resin composition layer for a light-shielding layer can also be adjusted together with the photopolymerizable monomer (C-1) in the component (C) described above. In the resin composition layer for a light-shielding layer, it is preferable to adjust the content in accordance with the content of the light-shielding component (D) described below. In other words, an increase in the content of the light-shielding component (D) reduces the content of the alkali-soluble resin (B) and the photopolymerizable monomer (C-1), which may affect curability, developability, etc., and therefore it is preferable to adjust the content of the alkali-soluble resin (B) and the photopolymerizable monomer (C-1) in accordance with the content of the light-shielding component (D).

[0063] <Shading component (D)> The light-shielding component (D) may contain any known light-shielding component without limitation, but is preferably at least one selected from the group consisting of organic black pigments, inorganic black pigments, and mixed-color pseudo-black pigments. Examples of organic black pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of inorganic black pigments include carbon black, chromium oxide, iron oxide, and titanium black. Examples of mixed-color pseudo-black pigments include pseudo-black pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. These light-shielding components (D) may be used alone or in combination of two or more. Among these light-shielding components, carbon black is more preferred from the viewpoints of its excellent light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins.

[0064] The carbon black is preferably untreated or oxidized carbon black. Here, "untreated" means that no special surface treatment such as oxidation treatment or resin coating treatment has been performed, and "oxidization treatment" means that the surface of the carbon black is treated with some kind of oxidizing agent before the dispersion step. Such untreated or oxidized carbon black has many acidic functional groups on its surface, so that untreated or oxidized carbon black is preferably used when utilizing these functional groups. Furthermore, when it is desired to further increase the resistance value of the cured film using carbon black, surface-coated carbon black in which the surface of the carbon black is coated with a dye, pigment, resin, or the like may be used.

[0065] When such a light-shielding component (D) is used, it can be appropriately set depending on the purpose and application of the present invention, and can be arbitrarily determined so as to obtain, for example, a desired light-shielding degree. The content of the light-shielding component (D) is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, of the solid content of the resin composition for light-shielding layer that forms the resin composition layer for light-shielding layer.

[0066] The light-shielding component (D) is usually dispersed in an organic solvent and mixed with other ingredients in the form of a dispersion, and a dispersant may be added in this case. The organic solvent may be any of those listed above. The dispersant may be any known compound used to disperse organic or inorganic pigments (e.g., compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion promoters, etc.), and the like, without any particular restrictions.

[0067] The average particle size of the light-shielding component (D) is preferably 10 to 300 nm, more preferably 30 to 250 nm, and even more preferably 50 to 220 nm. The average particle size can be determined by particle size distribution measurement using a dynamic light scattering method or the like.

[0068] <Photopolymerization initiator (E)> A photopolymerization initiator (E) is used in forming the resin composition layer for the light-shielding layer. As the photopolymerization initiator (E), any of those used in forming the resin composition layer for the antireflection layer can be used without limitation. As described above, the photopolymerization initiator (E) contains a sensitizer. In addition to this, the photopolymerization initiator (E) can contain the above-mentioned compound that can enhance the capabilities of the photopolymerization initiator or sensitizer.

[0069] The amount of the photopolymerization initiator (E) is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, per 100 parts by mass of the total of the alkali-soluble resin (B) and the photopolymerizable monomer (C-1).

[0070] <Average thickness> The average thickness of the resin composition layer for the light-shielding layer is preferably 0.1 to 30 μm. A more preferred average thickness is 0.2 to 20 μm, and a further preferred average thickness is 0.5 to 10 μm. When the average thickness of the resin composition layer for the light-shielding layer is less than the lower limit, the light-shielding properties tend to decrease. On the other hand, when the average thickness exceeds the upper limit, the time required for alkaline development increases, which is likely to lead to reduced productivity. The average thickness of the resin composition layer for the light-shielding layer can be determined by measuring the step between the surface of the resin composition layer for the light-shielding layer and the surface of the transparent substrate using a stylus-type step profiler, averaging the measurements to determine the average total thickness of the layer consisting of the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer, and then subtracting the average thickness of the resin composition layer for the antireflection layer from the average total thickness of the layers.

[0071] <Method for forming a resin composition layer for a light-shielding layer> The method for forming the resin composition layer for a light-shielding layer can be the same as the method for forming the resin composition layer for an antireflection layer described above, and examples thereof include a method in which the resin composition for a light-shielding layer is applied onto the resin composition layer for an antireflection layer, and then the organic solvent is removed by a heat treatment (pre-baking). The application method and the heating temperature and heating time in the pre-baking are preferably the same as those described above. Furthermore, the resin composition for a light-shielding layer is preferably used in the form of a solution containing an organic solvent, so that a uniform resin composition layer for a light-shielding layer can be formed. In this case, the content of the organic solvent and the viscosity of the resin composition for a light-shielding layer measured with a B-type or E-type viscometer are preferably the same as those described above.

[0072] <Other Components of Resin Composition Layer for Light-Shielding Layer> The resin composition layer for a light-shielding layer can also use, without limitation, the same components as those used in forming the resin composition layer for an antireflection layer. That is, the component (C) consisting of the above-mentioned photopolymerizable monomer (C-1) and / or epoxy compound (C-2), known curing agents and curing accelerators for epoxy compounds, and other components (various additives such as dispersants, polymerization initiators other than those mentioned above, chain transfer agents, non-photosensitive resins, antioxidants, plasticizers, fillers, coupling agents, surfactants, and dyes) can be used. The contents of these components are preferably the same.

[0073] <Solid content> The resin composition for a light-shielding layer that forms the resin composition layer for a light-shielding layer contains the above-mentioned components, and the solid content excluding the organic solvent (solid content includes monomers that become solid after drying or curing) is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably in the range of 10 to 30 mass %.

[0074] 3. Step of forming a light-shielding film consisting of an anti-reflection layer and a light-shielding layer As described above, after the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer are successively formed on a transparent substrate, these resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer are converted into an antireflection layer and a light-shielding layer, respectively, to form a light-shielding film consisting of an antireflection layer and a light-shielding layer.

[0075] The method of converting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer into an antireflection layer and a light-shielding layer, respectively, to form a light-shielding film consisting of the antireflection layer and the light-shielding layer can be as follows. That is, the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer are simultaneously exposed to light using a desired mask for forming a light-shielding film pattern, and the photosensitive portion (exposed portion) of the resin composition layer for an antireflection layer and the photosensitive portion (exposed portion) of the resin composition layer for a light-shielding layer are photocured. The exposure treatment conditions can be appropriately set depending on the types of alkali-soluble resin (B), photopolymerizable monomer (C-1), and photopolymerization initiator used, etc.

[0076] Next, the exposed resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer are subjected to a development process all at once to remove the resin composition layer in the unexposed parts of the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer, thereby simultaneously forming an antireflection layer and a light-shielding layer, respectively.

[0077] Furthermore, in order to sufficiently harden the formed antireflection layer and light-shielding layer, and to sufficiently remove the developing solution and improve the adhesion between the transparent substrate and the antireflection layer, the antireflection layer and the light-shielding layer are subjected to a heat curing treatment (post-baking), thereby obtaining a substrate with a light-shielding film, which has a light-shielding film (light-shielding film pattern) consisting of the antireflection layer and the light-shielding layer on the transparent substrate.

[0078] The development treatment method is not particularly limited, and a known development method can be used, and the development treatment conditions can be appropriately set depending on the type of alkali-soluble resin used, etc. As the alkaline developer in the development treatment (alkaline development treatment), a known alkaline developer such as an aqueous solution of a carbonate or hydroxide of an alkali metal or alkaline earth metal can be used.

[0079] The heating temperature and heating time in the post-baking can be appropriately set depending on the type of transparent substrate and resin composition used, and for example, when a transparent substrate having sufficient heat resistance such as a glass substrate is used, the heating temperature can be set to 180 to 250°C and the heating time can be set to 20 to 60 minutes.

[0080] In this way, a light-shielding film consisting of an antireflection layer and a light-shielding layer is formed. Here, the antireflection layer essentially contains the inorganic filler (A) and the alkali-soluble resin (B), and preferably has an average thickness of 0.01 to 0.4 μm. The light-shielding layer essentially contains the light-shielding component (D) and the alkali-soluble resin (B), and preferably has an average thickness of 0.1 to 30 μm. The average thickness of the light-shielding layer can be determined by measuring the step between the light-shielding layer surface and the transparent substrate surface using a stylus-type step profiler, averaging the measurements to determine the average thickness of the light-shielding film consisting of the antireflection layer and the light-shielding layer, and then subtracting the average thickness of the antireflection layer from the average thickness of the light-shielding film.

[0081] As described above, in the method for manufacturing a substrate with a light-shielding film of the present invention, the alkali-soluble resin (B), preferably the above-mentioned unsaturated group-containing alkali-soluble resin, is used in both the resin composition (layer) for the antireflection layer and the resin composition (layer) for the light-shielding layer, and therefore the exposure treatment and development treatment can be carried out simultaneously on the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer. As mentioned above, it has been confirmed that in the process of forming the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer, these layers are partially dissolved and mixed near the interface to form a layer, and it has also been confirmed that when converted into the antireflection layer and the light-shielding layer, a similar partially mixed layer is formed near the interface between these layers. In other words, although the detailed structure is not clear, the light-shielding film in the present invention is formed from such an antireflection layer and a light-shielding layer, and partially includes a structure in which the layers are partially mixed together as described above. [Example]

[0082] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0083] First, synthesis examples of unsaturated group-containing alkali-soluble resins corresponding to the alkali-soluble resin (B) of the present invention will be shown below. The resins in the synthesis examples were evaluated as follows.

[0084] [Measurement of epoxy equivalent weight] Using a potentiometric titrator, methyl ethyl ketone was used as the solvent, and tetraethylammonium bromide acetate solution was added, followed by measurement using a 0.1 mol / L perchloric acid-acetic acid solution in the potentiometric titrator.

[0085] [Acid value] The resin solution was dissolved in tetrahydrofuran and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per 1 g of solid content was taken as the acid value.

[0086] [Solid content concentration] 1 g of the resin solution, composition, etc. obtained in the synthesis examples was impregnated into a glass filter (mass: W0(g)), weighed (W1(g)), and heated at 160°C for 2 hours to obtain the mass (W2(g)). The mass was calculated from the following formula: Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0087] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuperH-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0088] [Synthesis of alkali-soluble resin] The abbreviations used in the synthesis examples of alkali-soluble resins are as follows: BPFE: Bisphenol fluorene epoxy (epoxy equivalent 254 g / eq, weight average molecular weight (Mw) 508, compound of general formula (I), in which A is a fluorene-9,9-diyl group, and R1 to R4 are hydrogen) BPF-EA: Reaction product of BPEF and acrylic acid (equivalent reaction product of epoxy and carboxyl groups) AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate TPP: Triphenylphosphine DCPMA: dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: styrene AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone SA: succinic anhydride TEA: Triethylamine

[0089] [Synthesis Example 1] A 1000 ml four-neck flask equipped with a reflux condenser was charged with 313.7 g of a 50% PGMEA solution of BPF-EA, 47.1 g of BPDA, 24.3 g of THPA, 0.43 g of TEAB, and 8.5 g of PGMEA, and the mixture was stirred at 120-125°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin solution. The solids concentration of the resin solution was 56.6 mass%, the weight-average molecular weight (Mw) was 3600, and the acid value (solids equivalent) was 89.4 mg KOH / g.

[0090] [Synthesis Example 2] PGMEA (300 g) was placed in a 1 L four-neck flask equipped with a reflux condenser, and the atmosphere in the flask was replaced with nitrogen and then heated to 120° C. A mixture of a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) dissolved in AIBN (10 g) was added dropwise from a dropping funnel to the flask over 2 hours, followed by stirring at 120° C. for an additional 2 hours to obtain a copolymer solution. Next, after replacing the atmosphere in the flask with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the resulting copolymer solution and stirred at 120 ° C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the moles of AA added) and TEA (0.5 g) were added to the resulting polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C for 4 hours to obtain an unsaturated group-containing alkali-soluble resin. The solids concentration of the resin solution was 56.0 mass%, the acid value (solids equivalent) was 76 mg KOH / g, and the Mw by GPC analysis was 5300.

[0091] [Preparation of Resin Composition Solution for Antireflection Layer and Light-Shielding Layer] The components and abbreviations used in preparing the resin composition solution for the antireflection layer and the resin composition solution for the light-shielding layer are as follows:

[0092] [Dispersion of inorganic filler (A)] A-1: A dispersion of 20% by mass of titania filler with a refractive index of 2.5 and an average particle size of 60 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-2: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 10 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-3: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 20 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-4: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 30 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-5: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 50 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-6: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 75 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass). A-7: A dispersion of 20% by mass of silica filler with a refractive index of 1.4 and an average particle size of 125 nm, and 5.0% by mass of a polymer dispersant in propylene glycol 1-monomethyl ether 2-acetate solvent (solid concentration 25% by mass).

[0093] [Alkali-soluble resin (B)] B-1: The unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 1 above. B-2: The unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 2 above.

[0094] [Photopolymerizable monomer, epoxy compound (C)] C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("DPHA" manufactured by Nippon Kayaku Co., Ltd.) C-2: Bisphenol fluorene epoxy (epoxy equivalent weight 254 g / eq, weight average molecular weight (Mw) 508) (BPFE).

[0095] [Light blocking component (D)] D-1: 20% by mass of carbon black pigment and 5.5% by mass of polymer dispersant dispersed in propylene glycol 1-monomethyl ether 2-acetate solvent (solids concentration 25.5% by mass)

[0096] [Photopolymerization initiator (E)] E-1: Oxime ester photoinitiator (Irgacure OXE01, manufactured by BASF Japan Ltd.)

[0097] [Organic solvent] Propylene glycol monomethyl ether acetate (PGMEA) Ethyl lactate (EL)

[0098] [Preparation of Resin Composition Solution] The resin compositions (solutions) for antireflection layers and resin compositions (solutions) for light-shielding layers according to Examples 1 to 13 and Comparative Examples 1 to 8 were prepared by blending the above-mentioned blending components in the proportions shown in Tables 1 and 2. All values ​​in Table 1 represent parts by mass (solid content) except for the inorganic filler dispersion, alkali-soluble resin solution, light-shielding component dispersion, and organic solvent.

[0099] [Table 1]

[0100] [Table 2]

[0101] A resin composition layer for an antireflection layer and a resin composition layer for a light-shielding layer were formed on a glass substrate as a transparent substrate using the resin composition (solution) for an antireflection layer and the resin composition (solution) for a light-shielding layer shown in Tables 1 and 2. A substrate with a light-shielding film was also produced using the formed layers. Specific evaluation methods and production procedures are as follows.

[0102] [evaluation] [Average thickness measurement] Using a stylus-type step shape measuring device ("P-10" manufactured by KLA Tencor Corporation), the step between the glass substrate surface and the surface of the resin composition layer for the anti-reflection layer was measured at two or more points under conditions of a measurement range of 500 μm, a scanning speed of 50 μm / sec, and a sampling rate of 20 Hz, and the average value was taken as the average thickness of the resin composition layer for the anti-reflection layer. In addition, after forming the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer, the height difference between the surface of the glass substrate and the surface of the resin composition layer for the light-shielding layer was measured at two or more points using the same method, and the average value was used as the average total thickness of the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer. Furthermore, even after the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer were subjected to a heat curing treatment (post-baking) at 230°C for 30 minutes, the height difference between the glass substrate surface and the light-shielding layer surface was measured at two or more points using the same method, and the average value was used as the average total thickness of the antireflection layer and the light-shielding layer.

[0103] [Measurement of Residual Film Ratio of Resin Composition Layer for Antireflection Layer] The solution of the resin composition for the anti-reflection layer was applied to a glass substrate using a spin coater, and the substrate was pre-baked at 90°C for 1 minute using a hot plate. After that, the substrate was left for 24 hours (Q-Time) or exposed to 10 mW / cm 2 in a deep UV irradiation device (Oak Manufacturing Co., Ltd.'s "Shutter-type UV Dry Processor VUE-3038"). 2 The coating was then irradiated for 25 seconds at an illuminance of 1.2 μm to form a resin composition layer for an antireflection layer having an average thickness of 1.2 μm. With the glass substrate still attached, this resin composition layer for an anti-reflection layer was immersed in PGMEA at 23°C for 5 seconds, and then dried in a vacuum drying (VCD) device ("SN120351" manufactured by Kawasaki Chemical Engineering Co., Ltd.) until the weight change was about 5% or less. The average thickness of the resulting film was measured, and the remaining film ratio was calculated using the following formula. The results are shown in Tables 3 and 4. Residual film rate (%) = 100 x (average thickness after immersion) / (average thickness before immersion) ...(*)

[0104] [Preparation of patterned laminated coating film (substrate with light-shielding film)] The resin composition solution for the anti-reflection layer was applied to a glass substrate using a spin coater, and the coating was pre-baked at 90°C for 1 minute using a hot plate. The pre-baked coating was then left for 24 hours (Q-Time), or the coating was exposed to 10 mW / cm irradiation using a deep UV irradiation device. 2 The resin composition solution for a light-shielding layer was applied onto the resin composition layer for an antireflection layer using a spin coater, and heated (prebaked) at 90°C for 1 minute using a hot plate to form a resin composition layer for a light-shielding layer having an average thickness of 1.05µm, which was used as a laminated coating film. The laminated coating film thus formed was covered with a negative photomask for forming an isolated fine line pattern of 1 to 20 μm, with the exposure gap adjusted to 100 μm, and exposed to 50 mJ / cm 2 The resin in the exposed area was photocured by irradiating it with ultraviolet light of 1 kgf / cm. After exposure, the laminated coating film was heated at 23°C with a 0.04% potassium hydroxide aqueous solution at 1 kgf / cm. 2 After the pattern began to appear, shower development was continued for another 20 seconds. 2 The unexposed portions of the laminated coating film were removed by spray washing with water at high pressure, forming a patterned laminated coating film on the glass substrate. The substrate was then subjected to a heat treatment (post-baking) at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a light-shielding film.

[0105] [Minimum adhesion] In the light-shielding film pattern of the obtained substrate with a light-shielding film, the minimum mask size at which no peeling of the isolated fine line pattern occurred was measured. The results are shown in Tables 3 and 4.

[0106] [Preparation of sample substrates for checking light blocking degree (unit: OD), reflectance, and coating unevenness] The resin composition solution for the anti-reflection layer was applied to a glass substrate using a spin coater, and the coating was pre-baked at 90°C for 1 minute using a hot plate. The pre-baked coating was then left for 24 hours (Q-Time) or exposed to 10 mW / cm irradiation using a deep UV irradiation device. 2 The resin composition solution for a light-shielding layer was applied onto the resin composition layer for an antireflection layer using a spin coater, and heated (prebaked) at 90°C for 1 minute using a hot plate to form a resin composition layer for a light-shielding layer having an average thickness of 1.05µm, which was used as a laminated coating film. The laminated coating film thus formed was irradiated with 50 mJ / cm 2 The resin in the exposed area was photocured by irradiating it with ultraviolet light of 1 kgf / cm. After exposure, the laminated coating film was heated at 23°C with a 0.04% potassium hydroxide aqueous solution at 1 kgf / cm. 2 After the pattern began to appear, shower development was continued for another 20 seconds. 2 The unexposed portions of the laminated coating film were removed by spray washing with water at high pressure, forming a patterned laminated coating film on the glass substrate. The substrate was then subjected to a heat treatment (post-baking) at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a light-shielding film.

[0107] [Light blocking degree (unit: OD) measurement] The optical density (OD value) of the obtained substrate with the light-shielding film was measured using an optical densitometer ("X-Rite361T(V)" manufactured by Sakata Inx Engineering Corporation), and this was corrected with the optical density (OD value) of the glass substrate to determine the light-shielding degree (OD value) of the light-shielding film. The OD value per unit average thickness (unit OD) was calculated using the following formula. The results are shown in Tables 3 and 4. (unit OD [- / μm]) = (OD value of light-shielding film) / (average thickness of light-shielding film)

[0108] [Reflectance measurement] The reflectance [%] of the glass surface side and the surface (film surface) opposite the glass surface side of the obtained substrate with a light-shielding film was measured using a spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science Corporation) under conditions of a C light source and a 2° field of view, and the reflectance was evaluated according to the following criteria: The following criteria were used to evaluate the degree of decrease in reflectance compared with that of Comparative Example 1, which did not have a layer of the resin composition for an antireflection layer (antireflection layer). The results are shown in Tables 3 and 4. (Reflectivity criteria) 〇 Verdict: A decrease of 1% or more is observed. △: A decrease of 0% or more but less than 1% is observed. × Verdict: No change.

[0109] [Uneven coating] The obtained substrate with the light-shielding film was visually inspected and evaluated according to the following criteria. The results are shown in Tables 3 and 4. (Criteria for judging uneven coating) ◯: No unevenness or abnormal appearance was observed on either the film surface or the glass surface of the substrate with the light-shielding film. △: Unevenness or abnormal appearance was observed on either the film surface or the glass surface of the light-shielding film-coated substrate. ×: Unevenness or abnormal appearance was observed on both the film surface and the glass surface of the substrate with the light-shielding film.

[0110] [Table 3]

[0111] [Table 4]

[0112] [Each evaluation result] As can be seen from the above results, it is confirmed that the reflectance can be suppressed on both the transparent substrate side and the opposite side (film surface) of the light-shielding film by the methods of Examples 1 to 13. In addition, the pattern adhesion (minimum mask size) and coating unevenness measurement results were also excellent.

[0113] In contrast, in Comparative Example 2 in which the refractive index of the inorganic filler (A) was outside the range of 1.2 to 1.8, and in Comparative Example 8 in which the solid content was less than 10 mass %, no effect of suppressing reflectance was observed.

[0114] In addition, in Comparative Example 3, in which inorganic filler (A) having an average particle diameter of 125 nm was used, and in Comparative Example 6, in which deep UV irradiation was performed in forming the resin composition layer for the antireflection layer, the residual film rate of the resin composition layer for the antireflection layer exceeded 90%.

[0115] In Comparative Example 4 in which the alkali-soluble resin (B) was not added, the solution was repelled on the substrate, and a resin composition layer for an antireflection layer could not be formed.

[0116] Furthermore, it is clear that in Comparative Example 7, in which the average thickness of the resin composition layer for an antireflection layer exceeds 0.4 μm, coating unevenness becomes apparent.

[0117] In particular, in Comparative Examples 3, 4, 5, and 6, where the residual film rate of the resin composition layer for the antireflection layer was outside the range of 10 to 90% or could not be measured, no effect of suppressing reflectance was observed. This is presumably because partial dissolution of the resin composition layer for the antireflection layer and the resin composition layer for the light-shielding layer did not occur sufficiently. [Industrial Applicability]

[0118] The substrate with a light-shielding film obtained by the production method of the present invention can be used as a black matrix used in a color filter or a touch panel, or as a partition material or pixel defining layer for separating colors or for shading in various multicolor display devices such as electroluminescent devices typified by organic EL elements, color liquid crystal display devices, or image sensors, and further as a display component such as a bezel surrounding the display part of a display.

Claims

1. A method for producing a substrate with a light-shielding film, which comprises providing a light-shielding film composed of an antireflection layer and a light-shielding layer on a transparent substrate, the method comprising: forming a resin composition layer for an antireflection layer on a transparent substrate; forming a resin composition layer for a light-shielding layer, which contains a light-shielding component (D), a photopolymerization initiator (E), and an alkali-soluble resin (B), on the resin composition layer for an antireflection layer; and a step of simultaneously subjecting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer to an exposure treatment, then simultaneously subjecting the resin composition layer for an antireflection layer and the resin composition layer for a light-shielding layer to a development treatment, and further subjecting the resin composition layer for an antireflection layer and the light-shielding layer to a heat-curing treatment, thereby forming a light-shielding film comprising an antireflection layer and a light-shielding layer, The method for producing a substrate with a light-shielding film, wherein the resin composition layer for an antireflection layer satisfies the following (1) to (3): (1) The composition contains an inorganic filler (A) having a refractive index of 1.2 to 1.8 and an average particle size of 10 nm or more and less than 125 nm, and an alkali-soluble resin (B), and the inorganic filler (A) is contained in an amount of 10 to 80 mass % in the solid content. (2) The average thickness is 0.01 to 0.4 μm. (3) When a film having an average thickness of 1.2 μm is immersed in propylene glycol monomethyl ether acetate for 5 seconds, the remaining film rate is 10 to 90%.

2. The method for manufacturing a substrate with a light-shielding film according to claim 1, characterized in that the light-shielding layer contains at least one light-shielding component (D) selected from the group consisting of organic black pigments, inorganic black pigments, and mixed-color pseudo-black pigments, and an alkali-soluble resin (B), and has an average thickness of 0.1 to 30 μm.

3. 2. The method for producing a substrate with a light-shielding film according to claim 1, wherein the resin composition layer for an antireflection layer contains a photopolymerizable monomer and / or an epoxy compound (C).

4. 2. The method for producing a substrate with a light-shielding film according to claim 1, wherein the inorganic filler (A) has an average particle size of 30 nm or more and less than 125 nm.

5. 2. The method for producing a substrate with a light-shielding film according to claim 1, wherein the resin composition layer for an antireflection layer has an average thickness of 0.01 to 0.2 μm.

6. 2. The method for producing a substrate with a light-shielding film according to claim 1, wherein the inorganic filler (A) is contained in an amount of 30 to 80 mass % of the solid content.

7. 2. The method for producing a substrate with a light-shielding film according to claim 1, wherein the alkali-soluble resin is an alkali-soluble resin containing an unsaturated group represented by the following general formula (II): 【Chemical 1】 [In formula (II), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ -, -CH ２ -, -C(CH ３ ) ２ represents -, -O-, a fluorene-9,9-diyl group or a direct bond; X represents a tetravalent carboxylic acid residue; Y １ and Y ２ each independently represents a hydrogen atom or —OC—Z—(COOH) m (wherein Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.

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