Black resin composition for light-shielding film, substrate with that light-shielding film by curing thereof, and color filter or touch panel using the substrate with that light-shielding film

Abstract

[Problem] A black resin composition for a light-shielding film (light-shielding film) for obtaining a black hardened film (light-shielding film) having a reflective color that is achromatic or has a bluish tint from achromatic, and a transparent substrate with the light-shielding film attached thereto formed on a transparent substrate. [Solution] A black resin composition for a light-shielding film containing as essential components (A) a resin curable by light or heat and / or a monomer curable by light or heat, (B) a dispersion containing black light-shielding particles formed by dispersing black light-shielding particles in a dispersion medium, and (C) a dispersion containing color-adjusting particles formed by dispersing color-adjusting particles in a dispersion medium. In addition, the ratio (DC / DB) of the average secondary particle diameter (DC) of the color-adjusting particles in component (C) and the average secondary particle diameter (DB) of the black light-shielding particles in component (B) is in the range of 0.2 to 1.2, and the ratio (mC / mB) of the mass (mC) of the color-adjusting particles included in component (C) and the mass (mB) of the black light-shielding particles included in component (B) is in the range of 0.03 to 0.2.

Description

Technology Field

[0001] The present invention relates to a black resin composition for a light-shielding film, a light-shielding film attachment substrate having a light-shielding film cured from the composition on a transparent substrate such as glass, and a color filter for a display such as an LCD and a touch panel for a display device having the light-shielding film attachment substrate as a component. More specifically, the invention relates to a black resin composition that is cured by light or heat suitable for forming a fine light-shielding film on a transparent substrate, and a light-shielding film attachment substrate having the light-shielding film formed at a selective location. Background Technology

[0002] Color liquid crystal panels are used in all fields, including liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. A color liquid crystal panel has a structure in which a substrate with a color filter is bonded to a counter substrate (TFT substrate) using a sealing material, and liquid crystal is filled between the two substrates. Among these, regarding the manufacturing method of the color filter, a method is typically used in which a black matrix is ​​formed on the surface of a transparent substrate, such as glass or a plastic sheet, to enhance contrast by suppressing color mixing between red, green, and blue, and subsequently, other colors of red, green, and blue, which are responsible for expressing all natural colors, are sequentially formed in color patterns such as stripes or mosaics. Furthermore, in touch panels, when forming the touch panel circuit on the front glass, a method is employed in which a light-blocking layer is formed in a frame shape around the periphery of the screen to hide lead wiring, such as metal.

[0003] Carbon black, which has high light-blocking properties, is primarily used as a light-blocking material for the black matrix of color filters or for the light-blocking film forming the frame of touch panels. However, the reflected light from carbon black is typically not an uncolored black—that is, a grayscale black—but is usually tinted with a slightly brownish hue. Consequently, this tinted light, which deviates from the grayscale, leaks out, causing a problem where the desired color cannot be displayed when black or low-luminosity colors are displayed in the color filter. Furthermore, there is an issue where the color of the black bezel (the frame surrounding the display screen of a liquid crystal display or touch panel) is misaligned when the power is off, resulting in poor aesthetics. As demands for design become more diverse, the need to adjust the color of black is steadily increasing. Additionally, black light-blocking materials other than carbon black are also mostly not grayscale black; therefore, technology to adjust them to grayscale black is required. Recently, there has been a demand to make the black matrix "neutral black" (uncolored black: achromatic) to improve the visibility and aesthetic appeal of liquid crystal panels. Additionally, in the case of touch panels, it is sometimes necessary to match the frame portion to the color of the black bezel, and in such cases, the touch panel frame must be neutral black.

[0004] In order to realize neutral black, Patent Document 1 states that it is necessary to match the chromaticity coordinates in the XYZ color system of the transmitted light and / or reflected light of a resin black matrix in a C light source or an F10 light source with the chromaticity coordinates of the light source. However, the technology specifically described is a technology for adjusting the chromaticity by dispersing an organic pigment consisting of a blue or purple pigment, which is the complementary color of the brown color, with respect to carbon black and the brown color of said carbon black that deviates from achromatic color, and it is necessary to add a large amount of the complementary color pigment. However, particularly when the carbon black content in the resist is high to enhance light-blocking properties, or when a large amount of complementary pigment is added, the mixing ratio of binder resins or curable monomer components that contribute to curability becomes relatively small. Consequently, it becomes difficult for the coating film to cure sufficiently, leading to problems such as reduced adhesion between the film and the glass substrate, making delamination more likely, and adversely affecting reliability characteristics, such as a decrease in resistivity and adhesion after environmental resistance testing. Furthermore, only the chromaticity adjustment of transmitted light is described, and the chromaticity adjustment of reflected light is not specifically indicated.

[0005] In addition, as a method for making the reflective color neutral black, a technique of adding a red pigment or a yellow pigment, which is a coloring pigment, to a light-blocking material such as carbon black or titanium nitride has been disclosed (Patent Documents 2 and 3), but the dispersion state of the light-blocking material and the coloring pigment used is not mentioned, so there is a growing demand for a technique that can reliably adjust the reflective color to a certain degree of bluish tint from the desired neutral black or a neutral black with a desirable tendency. Prior art literature

[0006] WO95 / 35525 Pamphlet Japanese Patent Publication No. 2011-227467 Japanese Patent Publication No. 2014-119640 Effects of the invention

[0019] (Effect of the invention)

[0007] The present invention was conceived in consideration of the various drawbacks of such technology, and its purpose is to provide a black light-blocking film with high light-blocking properties, as well as a light-blocking film such as a black matrix for a color filter and a substrate to which the light-blocking film is attached, wherein the reflected light is adjusted to a color tone such as achromatic black or black with a slightly bluish tint. That is, by using a specific black resin composition for a light-blocking film formed by dispersing a light-blocking material in a resin, the L of the reflected light * a * b * Chromaticity coordinates in a color system (a * , b * One objective is to obtain a light-blocking film of )≈(0.0, 0.0), and practically speaking, since it is important to be able to adjust the color to match the color of the black bezel, a * , b * The purpose is to obtain a light-blocking film that matches the color of a black bezel, etc., by adjusting the color to the negative side (minus side).

[0008] As a result of conducting diligent research to solve the problems of the prior art described above, the inventors discovered that by forming a black resin composition using specific color-adjusting particles in addition to black light-blocking particles such as carbon black and titanium black, and a curable resin or curable monomer, the color of the light-blocking film can be adjusted to a neutral color or a black color with a bluish tint. Furthermore, they discovered that in the black resin composition, the ratio of the average secondary particle diameter of the black light-blocking particles to the average secondary particle diameter of the color-adjusting particles is set to a specific range, and the mass ratio of the mass of the black light-blocking particles to the mass of the color-adjusting particles is set to a specific range, thereby reliably realizing the adjustment of the color. At this time, when the color of the color-adjusting particles is such that carbon black deviates from achromatic to brown, instead of mixing in blue or purple pigments that are in a complementary (opposite) relationship with the deviant color, it was discovered that by incorporating a small amount of yellow or orange pigments that are in a similar color relationship with the deviant color, the color of the light-blocking film can be adjusted to achromatic or bluish black while maintaining the film characteristics and reliability after curing, and thus the present invention was completed.

[0009] In other words, the gist of the present invention is as follows. That is,

[0010] (1) The present invention is a black resin composition for a light-shielding film comprising as essential components (A) a light- or heat-curable resin and / or a light- or heat-curable monomer, (B) a black light-shielding particle-containing dispersion in which black light-shielding particles are dispersed in a dispersion medium, and (C) a color-adjusting particle-containing dispersion in which color-adjusting particles are dispersed in a dispersion medium.

[0011] (2) The present invention also relates to the black resin composition for a light-blocking film of (1), wherein the average secondary particle diameter (D) of the color-adjusting particles in component (C) C Average secondary particle diameter of black light-blocking particles in ) and (B) components (D BThe ratio of ) (D C / D B ) is in the range of 0.2 to 1.2, and also the mass (m) of the color-adjusting particles included in component (C) C The mass of black light-blocking particles included in ) and component (B) (m B The ratio of )(m C / m B It is a black resin composition for a light-shielding film characterized by having a range of 0.03 to 0.2.

[0012] (3) The present invention is also a black resin composition for a light-blocking film of (1) or (2), characterized in that the black light-blocking particles are carbon black particles.

[0013] (4) The present invention is also a black resin composition for a light-blocking film of any one of (1) to (3), characterized in that the color-adjusting particles are CI Pigment Yellow 139, which is a yellow pigment, and / or CI Pigment Orange 61, which is an orange pigment.

[0014] (5) The present invention also comprises a black resin composition for a light-shielding film as described in any one of (1) to (4), wherein (A) as a component, a polymerizable unsaturated group-containing alkali-soluble resin and a polymerizable monomer having an ethylenically unsaturated double bond are used, and (D) a solvent and (E) a photopolymerization initiator are used, wherein the polymerizable unsaturated group-containing alkali-soluble resin is 10 to 60 mass% in the solid content containing the polymerizable monomer that becomes solid after photocuring, and the polymerizable monomer having an ethylenically unsaturated double bond is 10 to 60 mass parts per 100 mass parts of the polymerizable unsaturated group-containing alkali-soluble resin, and (E) is 2 to 50 mass parts per 100 mass parts of the total amount of the polymerizable unsaturated group-containing alkali-soluble resin and the polymerizable monomer having an ethylenically unsaturated double bond, and further, the black light-shielding particles in component (B) of the solid content are 30 to 60 mass%, and component (C) of the solid content This is a black resin composition for a light-blocking film characterized by having 1 to 15 mass% of color-adjusting particles in it.

[0015] (6) The present invention is a black resin composition for a light-blocking film of (5) characterized by using a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) a tetracarboxylic acid or its acid dihydride with a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and a monocarboxylic acid containing an unsaturated group as a polymerizable unsaturated group-containing alkali-soluble resin.

[0016] (7) The present invention is also a light-shielding substrate obtained by applying and curing a black resin composition for a light-shielding film of any one of (1) to (6) on one side of a transparent substrate, and b of the light-shielding substrate in the CIE Lab color space display system measured from the side opposite to the side of the transparent substrate where the light-shielding film is applied. * The value is -1.0 * It is a substrate with a light-shielding film attached, characterized by satisfying <+0.2.

[0017] (8) The present invention is also a color filter having a light-blocking substrate of (7).

[0018] (9) The present invention is also a touch panel having a light-shielding substrate of (7).

[0020] By using the black resin composition of the present invention, it is possible to form a black cured film (light-blocking film) on a transparent substrate, wherein the reflective color is controlled to be achromatic or a color such as black with a bluish tint from achromatic. The transparent substrate with the light-blocking film attached, on which the light-blocking film is formed, can be applied to a color filter or touch panel for a display device. That is, according to the present invention, it is possible to design a color filter or touch panel with excellent design quality even when the display screen is not illuminated. Specific details for implementing the invention

[0021] The present invention will be described in detail below.

[0022] ​As the component (A) of the black resin composition of the present invention, the light or heat-curable resin and / or light or heat-curable monomer may be used if it is a resin or monomer having at least one cyclic reactive group, such as an ethylenically unsaturated double bond such as a (meth)acrylic group or a vinyl group, or an epoxy group or an oxetane group, within the molecule, which exhibits a curing reaction by heat or light.

[0023] (A) As a compound having an ethylenically unsaturated double bond as a component, there is (A-1) a resin having an ethylenically unsaturated double bond and (A-2) a polymerizable monomer having an ethylenically unsaturated double bond, and (A-1) or (A-2) may be used alone or mixed in any proportion, taking into account process conditions such as coating, conditions for curing with light or heat, and physical properties of the cured product.

[0024] (A-1) As a component, a curable resin having an unsaturated double bond that hardens by light or heat, obtained by reacting a copolymer synthesized using 3 to 5 types of polymerizable monomers containing at least one type having a carboxyl group from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate (hereinafter, these may be collectively described as “alkyl (meth)acrylate,” etc.), cyclic cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and styrene, with a carboxyl group having at least one ethylenically unsaturated double bond having an epoxy group or an isocyanate group, such as glycidyl methacrylate, isocyanate ethyl acrylate, or methacryloyl isocyanate, etc. Examples include. As a curable resin having such a structure, it is preferable to use a curable resin having a weight average molecular weight of 5,000 to 100,000 and an acid value of 50 to 150 due to its heat resistance and developability.

[0025] In addition, other examples of component (A-1) include epoxy(meth)acrylate type curable resins obtained by reacting (meth)acrylic acid with epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycityl ester, aliphatic or alicyclic epoxy resin, amine type epoxy resin, triphenolmethane type epoxy resin, or dihydroxybenzene type epoxy resin. An epoxy(meth)acrylate acid adduct obtained by further reacting acid monohydride and acid dihydride with this epoxy(meth)acrylate type curable resin can be suitably used to form a resin composition capable of pattern formation by alkaline development in photolithography. In this case, the suitable weight average molecular weight is 2000 to 20000, and the acid value is 50 to 150.

[0026] As an epoxy(meth)acrylate acid adduct obtained by further reacting an acid monohydride and an acid dihydride with the above-mentioned epoxy(meth)acrylate type curable resin, which is a preferred example of using the present invention in a photolithography method, the epoxy(meth)acrylate acid adduct is an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or a tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dihydride with a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and a monocarboxylic acid containing an unsaturated group. Here, it is preferable that the molar ratio of (a) / (b) is 0.01 to 10.

[0027] Examples of bisphenols that serve as raw materials for this epoxy(meth)acrylate acid adduct 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-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, Bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)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, Examples include 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-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc., and derivatives thereof. Among these, those having a fluorene 9,9-diyl group are particularly suitable for use.

[0028] Next, the above bisphenols are reacted with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves the oligomerization of the diglycidyl ether compound, an epoxy compound of the following general formula (I) is obtained.

[0029]

[0030] In the formula of 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, and 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 a number from 0 to 10. Preferably, R1, R2, R3, and R4 are hydrogen atoms, and preferred A is a fluorene 9,9-diyl group. Also, since l is usually a mixture of multiple values, the average value is 0 to 10 (not limited to integers), but the preferred average value of l is 0 to 3. If the value of l exceeds the upper limit, when using a black resin composition made with an alkali-soluble resin synthesized using the above epoxy compound, the viscosity of the composition becomes excessively high, making it difficult to apply, or sufficient alkali solubility cannot be imparted, resulting in very poor alkali development performance.

[0031] Next, a reaction product having a hydroxyl group obtained by reacting acrylic acid or methacrylic acid or both as an unsaturated monocarboxylic acid with a compound of general formula (I) is reacted with (a) a dicarboxylic acid or a tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dihydride, preferably in a range where the molar ratio of (a) / (b) is 0.01 to 10, to obtain a polymerizable unsaturated alkali-soluble resin having the structure of an epoxy(meth)acrylate acid adduct represented by the following general formula (II).

[0032]

[0033] (In the formula, R1, R2, R3, R4 and A are defined identically to general formula (I), R5 represents a hydrogen atom or a methyl group, X represents a tetravalent carboxylic acid residue, and Y1 and Y2 are each independently a hydrogen atom or -OC-Z-(COOH) m (where Z represents a divalent or trivalent carboxylic acid residue, m represents a number from 1 to 2, and n represents a number from 1 to 20.)

[0034] This epoxy (meth)acrylate acid adduct (II) is a polymerizable unsaturated group-containing alkali-soluble resin having both an ethylenically unsaturated double bond and a carboxyl group, so when the black resin composition of the present invention is used in an alkali developing type photolithography method (A-1), it provides excellent photocurability, good developability, and patterning characteristics, and a good pattern shape is obtained.

[0035] (a) As the dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy(meth)acrylate acid adduct of general formula (II), chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or tricarboxylic acid or its acid anhydride, aromatic dicarboxylic acid or tricarboxylic acid or its acid anhydride is used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride, compounds such as 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, diglycolic acid, etc. are used, and may also be a dicarboxylic acid or tricarboxylic acid or its acid anhydride to which any substituent has been introduced. In addition, as a dicarboxylic acid or tricarboxylic acid or its acid anhydride, examples include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norborneneindicarboxylic acid, and may also be a dicarboxylic acid or tricarboxylic acid or its acid anhydride to which any substituent has been introduced. In addition, as an aromatic dicarboxylic acid or tricarboxylic acid or its acid anhydride, examples include compounds such as phthalic acid, isophthalic acid, and trimellitic acid, and may also be a dicarboxylic acid or tricarboxylic acid or its acid anhydride to which any substituent has been introduced.

[0036] In addition, as (b) tetracarboxylic acid or its acid dihydride used in the epoxy(meth)acrylate acid adduct of general formula (II), chain hydrocarbon tetracarboxylic acid or its acid dihydride, alicyclic tetracarboxylic acid or its acid dihydride, or aromatic polycarboxylic acid or its acid dihydride is used. Here, as for the chain hydrocarbon tetracarboxylic acid or its acid dihydride, examples include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and it may also be a tetracarboxylic acid or its acid dihydride to which a substituent has been introduced. In addition, examples of alicyclic tetracarboxylic acids or their acid dihydrides include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornenetetracarboxylic acid, and may also be tetracarboxylic acids or their acid dihydrides to which substituents have been introduced. In addition, examples of aromatic tetracarboxylic acids or their acid dihydrides include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid or their acid dihydrides, and may also be tetracarboxylic acids or their acid dihydrides to which substituents have been introduced.

[0037] The molar ratio (a) / (b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dihydride used in the epoxy(meth)acrylate acid adduct of general formula (II) is preferably in the range of 0.01 to 10, and more preferably in the range of 0.1 to 3.0. If the molar ratio (a) / (b) deviates from the above range, the optimal molecular weight is not obtained, and the alkali developability, heat resistance, solvent resistance, pattern shape, etc. of the black resin composition used as (A-1) deteriorate, which is undesirable. In addition, as the molar ratio (a) / (b) becomes smaller, the molecular weight tends to increase and alkali solubility tends to worsen.

[0038] In addition, the epoxy(meth)acrylate acid adduct of general formula (II) preferably has a weight average molecular weight (Mw) between 2000 and 10000, and particularly preferably between 3000 and 7000. If the weight average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development of the black resin composition used as (A-1) cannot be maintained, and pattern peeling occurs. Also, if the weight average molecular weight (Mw) exceeds 10000, development residue or residual film in unexposed areas is likely to remain. In addition, it is preferable that the acid value be in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, the alkali development of the black resin composition used as (A-1) tends to worsen, so special development conditions such as strong alkali become necessary. On the other hand, if it exceeds 200 mg KOH / g, the penetration of the alkali developer into the black resin composition used as (A-1) becomes excessively fast, causing peeling, so neither is desirable.

[0039] The epoxy(meth)acrylate acid adduct of general formula (II) used in the present invention can be manufactured by the above-described process by a known method, for example, by the method described in Japanese Patent Publication No. Hei 8-278629 or Japanese Patent Publication No. 2008-9401. First, as a method for reacting an epoxy compound of general formula (I) with a monocarboxylic acid containing an unsaturated group, for example, there is a method of adding a monocarboxylic acid containing an unsaturated group to the epoxy group of the epoxy compound in a saccharide mole of the epoxy group and a solvent, and then heating and stirring at 90 to 120°C while blowing air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.) to cause the reaction. Next, as a method for reacting an acid anhydride with the hydroxyl group of the reaction product, an epoxy acrylate compound, there is a method of adding a predetermined amount of the epoxy acrylate compound, an acid dihydride, and an acid monohydride into a solvent and reacting them by heating and stirring at 90 to 130°C in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.).

[0040] In addition, (A-2) as a polymerizable monomer having an ethylenically unsaturated double bond (photopolymerizable monomer), for example, (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, or 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, trimethylol ethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Examples of (meth)acrylic acid esters include pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc., and one or more of these may be used as (A-2) components. In addition, it is preferable to use a polymerizable monomer having an ethylenically unsaturated double bond that has three or more polymerizable groups and is capable of crosslinking molecules of a photo- or thermosetting resin (an alkali-soluble resin containing polymerizable unsaturated groups when used in the photolithography method). In addition, (A-2) when the polymerizable monomer having an ethylenically unsaturated double bond is used as a black resin composition used in the photolithography method, a monomer that does not have a free carboxyl group is used.

[0041] In addition, as component (A), compounds having at least one cyclic reactive group, such as (A-3) epoxy group or oxetane group, in the molecule can be cited. In this specific example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, polymers containing (meth)acrylic acid glycidyl as a unit, alicyclic epoxy compounds represented by 3,4-epoxycyclohexanecarboxylic acid (3',4'-epoxycyclohexyl) methyl, polyfunctional epoxy compounds having a dicyclopentadiene backbone (e.g., HP7200 series from DIC), 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., "EHPE3150" from Daicel), epoxylated polybutadiene (e.g., Examples include Nippon Soda's "NISSO-PB·JP-100"), epoxy compounds having a silicon backbone, etc.

[0042] (A) For the component, only one of the compounds having an ethylenically unsaturated double bond such as (A-1) and (A-2) and (A-3) a compound having a cyclic reactive group may be used, or a mixture of both compounds may be used.

[0043] In addition, when using a compound having an ethylenically unsaturated double bond as component (A), it is preferable to use a photopolymerization initiator, a thermal polymerization initiator, etc., which generate radicals, cations, anions, etc., by ultraviolet rays or heat. In addition, when using a compound having a cyclic reactive group (A-3), it is preferable to use a compound that reacts with the cyclic reactive group by light or heat, such as a compound having a carboxyl group, an amino group, a hydroxyl group, or a thiol group, as a curing agent.

[0044] It is preferable to select a cured product of component (A) with a refractive index in the range of 1.48 to 1.6. For example, in the case of an acrylic resin-based cured product, the refractive index is 1.49 to 1.55 and is adjusted by copolymerization with styrene monomers having aromatic groups in their chemical structure. In the case of an epoxy resin-based product, it is 1.50 to 1.60, and the refractive index is higher when using a bisphenol-based epoxy resin or an aromatic acid anhydride curing agent, and relatively lower when using an aliphatic epoxy resin, alicyclic epoxy resin or alicyclic acid anhydride curing agent.

[0045] In addition, regarding the content of component (A), it should be in the range of 25 to 60 mass% of the solid content of the black resin composition excluding the solvent component (including the curable monomer component that becomes a solid after curing), and it is preferable that it be in the range of 35 to 55 mass%.

[0046] As black light-blocking particles included in component (B), black organic pigments or inorganic pigments may be used without particular limitation. Examples of black organic pigments include perylene black, cyanine black, aniline black, lactam black, etc. Examples of inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, etc. These black light-blocking particles may be used individually or two or more types may be appropriately selected and used. Black pigments that absorb visible light with a refractive index exceeding 1.6 are primarily used from the perspective of light-blocking rate in the target thin film and storage stability of the light-blocking film composition. Carbon black is preferred as the black light-blocking particle used in the present invention. Any of the following may be used as carbon black: lamp black, acetylene black, thermal black, channel black, furnace black, etc. In addition, to adjust light-blocking properties, one or more types of other light-blocking components, such as black dyes, may be used in combination, but black light-blocking particles are preferably 60% or more of the light-blocking components. For example, if a large amount of light-blocking components based on pseudo-black organic pigments or dyes are used, the light-blocking rate decreases, making it difficult to obtain the desired light-blocking rate (OD).

[0047] These black light-shielding particles or other light-shielding components are dispersed in a bead mill together with a dispersion medium containing a solvent or a dispersant such as a polymer dispersant to form a dispersion containing black light-shielding particles (dispersion containing black light-shielding particles), and the black resin composition for a light-shielding film according to the present invention can be prepared by mixing this with component (A) and component (C) described below. The average secondary particle diameter (D) of the black light-shielding particles dispersed in this dispersion BThe particle size is prepared to be 60 nm to 150 nm, preferably 80 nm to 120 nm. In addition, in the present invention, "average secondary particle diameter" refers to the value of the average particle diameter obtained by the cumulant method, measured by dynamic light scattering after dilution with a dispersion solvent or an equivalent solvent. Furthermore, in the case of black light-shielding particles, such as carbon black, where fine primary particles are connected in a grape cluster shape, the particle diameter in that shape (average secondary particle diameter) is important because it exhibits physical properties. Also, even if the particles are not connected in a grape cluster shape, the finer the particle diameter (average primary particle diameter), the more likely they are to aggregate in the dispersion, and thus the particle diameter in that aggregated state (average secondary particle diameter) becomes important. Therefore, in the present invention, the particle diameter in the dispersion is defined as the average secondary particle diameter.

[0048] For example, in carbon black, it is a value measured at a particle concentration of 0.1 mass% in propylene glycol monomethyl ether acetate solvent. Average secondary particle diameter (D B If ) is less than 60 nm, the addition of polymer dispersants required to increase the concentration of black light-blocking particles to achieve a high light-blocking rate increases, or an increase in viscosity is likely to occur during storage. Average secondary particle diameter (D B If ) exceeds 150 nm, the surface smoothness of the formed light-shielding film is undesirable, and the linearity of the pattern edge is also damaged when formed by photolithography.

[0049] In addition, for a light-shielding film for a touch panel and a black matrix for a color filter, the light-shielding degree (OD=-log[transmittance]) is required to be OD4 or higher, and on the other hand, a thin film thickness of 3㎛ or less, preferably 2㎛ or less, is required. The reason is to prevent disconnection when connecting the metal wiring on the light-shielding film of the touch panel and the conductive film on the touch panel in the touch panel, and to flatten the color filter in the black matrix. To obtain a high light-shielding degree even with such a thin light-shielding film, it is preferable to, for example, have carbon black-based black light-shielding particles in an amount of 35% or more and 70% or less with respect to the total solid content in the composition.

[0050] (C) As yellow pigments and orange pigments usable in color-adjusting particles included in component (C), for example

[0051] CI pigment yellow (PY) 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, and 173, etc.;

[0052] CI pigment orange (PO) 36, 43, 51, 55, 59, 61, 71, 73, etc.;

[0053] Examples include these, but among them, CI Pigment Yellow efficiently maintains an OD value of 4.0 or higher b * It is desirable to be able to subtract the value. In addition, specific examples that can be particularly preferably used as particles for color composition include PY139 or PO61.

[0054] For example, when using carbon black as a black light-blocking particle, since carbon black typically has a brown-based reflective color, pigments of the same color family, such as PY139 and PY150, are preferred. This "same color family" refers to a color that is the same as the hue or chromaticity of the black light-blocking particle when it deviates from achromatic. For example, if the black light-blocking particle deviates to a brown hue or chromaticity, the orange or yellow hue or chromaticity located at the same position on the color wheel is the same color family. Furthermore, "opposite color to the light-blocking material" refers to a color that is the opposite of the hue or chromaticity when the black light-blocking particle deviates from achromatic. For example, if the light-blocking material deviates to a brown hue or chromaticity, the blue or purple hue or chromaticity located near the diagonal on the color wheel is the opposite color. In other words, regarding carbon black, which is one of the black light-blocking particles and has a color that deviates from achromatic to brown, it has traditionally been thought that it is mixed with pigments / dyes that are complementary (opposite) to that deviate color, such as "blue pigments / dyes" or "purple pigments / dyes."

[0055] These color-adjusting particles can be dispersed in a bead mill together with a dispersion medium containing a solvent and a dispersant such as a polymer dispersant to form a dispersion containing color-adjusting particles (dispersion containing color-adjusting particles), and the black resin composition for a light-shielding film according to the present invention can be prepared by mixing this with component (A) and component (B). In addition, the average secondary particle diameter (D) of the color-adjusting particles dispersed in this component (C) C Regarding ), the average secondary particle diameter (D) of the black light-shielding particles in the above (B) component B Ratio with ) (D C / D B Ensure that ) is in the range of 0.2 to 1.2. This average secondary particle diameter (D C ) is the value of the average particle diameter obtained by the cumulant method, measured by dynamic light scattering after dilution with a dispersion solvent or an equivalent solvent.

[0056] For example, for yellow pigment particles, the dispersion is a measured value at a particle concentration of 0.1 to 1.0 mass%. Ratio of average secondary particle diameters (D C / D B If ) exceeds 1.2, b * The effect of minubling the value is practically not observed. In addition, the ratio of the average secondary particle diameter (D C / D B If ) falls below 0.2, the dispersion stability in the composition decreases. The average secondary particle diameter (D) of a carbon black-containing dispersion used for shading films B Since ) is 60–150 nm, D C It is difficult to prepare a dispersion containing a yellow pigment with a g of 30 nm or less. D C The preferred average secondary particle diameter is 60 to 150 nm, more preferably 80 to 120 nm.

[0057] In addition, in the present invention, the mass (m) of the color-adjusting particles (solids) included in component (C) of the composition is C The mass (m) of the black light-blocking particles (solids) included in ) and component (B). B The mass ratio of ) (m C / m B Make sure that ) is in the range of 0.03 to 0.2. This m C / m B If ga is below 0.03, b * No reduction effect is observed, and if it exceeds 0.2, the light blocking rate (OD / ㎛) decreases.

[0058] However, in a light-shielding substrate formed as a cured film of the present composition, the color-correcting particles are b *The following is hypothesized as the mechanism exhibiting the reduction function. That is, in a substrate with a light-shielding film attached, a portion of the light incident from the transparent substrate side is reflected and scattered solely by particles dispersed at the transparent substrate interface and within the light-shielding film in its vicinity, and exits toward the transparent substrate side. Scattering by fine particles occurs when the particle diameter is smaller than the wavelength of light; particularly in the Rayleigh scattering region, the wavelength dependence of backscattering with respect to the direction in which light is incident on the fine particles becomes significant. Backscattering caused by yellow or orange pigments, which have a particle diameter equal to or smaller than that of carbon black particles, is thought to scatter more light in the blue region—their complementary color—backward.

[0059] Color adjustment of the above shading film (b * In order to effectively exert the mechanism of (adjusting to the negative side), it is necessary to stably disperse the color-adjusting particles together with the black light-blocking particles without self-aggregating, both within the composition and within the film coated on the transparent substrate. Therefore, the black light-blocking particles and the color-adjusting particles in the present invention are dispersed in a bead mill together with a polymer dispersant in an organic solvent and provided as a dispersion.

[0060] The black resin composition for a light-blocking film of the present invention may contain one or more types of (D) solvents for the purpose of dissolving a curable resin, etc. by light or heat, and dispersing black light-blocking particles or color-adjusting particles, etc., and is not particularly limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; 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; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol; glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; ethyl acetate; butyl acetate, Examples include acetic acid esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By using several types of these and dissolving and mixing them, a uniform composition can be obtained in which black light-blocking particles or color-adjusting particles are stably dispersed.

[0061] The content of such solvent is preferably in the range of 5 to 2000 parts by mass per 100 parts by mass of the black resin composition, and preferably 50 to 1000 parts by mass, and is used for purposes such as adjusting to an appropriate solid content and solution viscosity by a method of coating on a transparent substrate.

[0062] When applying the black resin composition of the present invention as a photocurable composition (black photosensitive resin composition) to a photolithography method, etc., it is necessary to include (E) a photopolymerization initiator. As this (E) photopolymerization initiator, for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin isobutyl ether, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, Non-imidazole compounds such as 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole and 2,4,5-triarylbiimidazole, halomethylthiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, Halomethyl-S-triazine compounds such as 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(trichloroR-methyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime),o-acyloxime compounds such as 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)butane-1-onoxime-o-acetate, sulfur compounds such as benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, Examples include thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Among these, it is preferable to use o-acyloxime-based compounds from the perspective of facilitating the acquisition of a high-sensitivity black photosensitive resin composition. Additionally, two or more of these photopolymerization initiators may be used. Furthermore, the term "photopolymerization initiator" as used in the present invention is used to include sensitizers.

[0063] In addition, the black resin composition for a light-shielding film of the present invention may include additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant, as needed. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, etc. Examples of antioxidants include hindard phenol-based compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of antifoaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. In addition, examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

[0064] In addition, for light-shielding films for display devices such as LCDs and touch panels that require a design ranging from achromatic to black with a bluish tint, there is a request to increase the design quality by setting the reflectance of the light-shielding film to an appropriate range. For this purpose, inorganic particles such as silica may be used as additives in the composition of the present invention.

[0065] As a method for applying a black resin composition for a light-shielding film onto a transparent substrate, in addition to known solution immersion and spray methods, any one of the following methods may be employed: using an inkjet machine, a roller coater, a land coater, a slit coater, or a spinner. The viscosity is adjusted to an appropriate level to obtain a good coating film according to the solvent, and after applying to a desired thickness by these methods, a dry film is formed by removing the solvent under heating or reduced pressure (pre-baking). Subsequently, a substrate with a light-shielding film attached is prepared by curing by light and / or heat.

[0066] There is a photolithography method for forming a light-shielding film pattern on a transparent substrate, wherein the composition of the present invention is applied to a transparent substrate, dried, and then irradiated with ultraviolet light through a photomask onto the film, the unexposed portions are removed by a developer, and heat treatment is performed. Additionally, there are printing methods using transfer plates, such as screen printing, intaglio printing, and gravure printing. Furthermore, recently, inkjet printing has been conceived as a digital printing method that does not require a mask or printing plate. The black resin composition for a light-shielding film of the present invention is applicable to any pattern forming method or printing method, and in order to make it a resin composition having viscosity and surface tension suitable for each printing method, the above-described curable resin / curable monomer or additives such as solvents and surfactants are selected. Additionally, a printing press is selected according to the printing precision and resolution of the light-shielding film pattern.

[0067] For example, when forming a light-blocking film using an inkjet printing method, the composition of the present invention has less re-aggregation of particles such as light-blocking black particles or color-adjusting particles contained therein, so there is less clogging of the inkjet nozzle during intermittent ejection, and also contributes to the stability of the pattern film thickness during continuous printing because the viscosity remains stable over time. Regarding the inkjet device, there are no particular restrictions as long as the amount of the composition ejected is adjustable, but the physical properties of the ink composition that stably forms droplets in an inkjet head of a commonly used piezoelectric element vary depending on the configuration of the head, but it is preferable that the viscosity be 3 mPa·sec to 150 mPa·sec at the temperature inside the head, and preferably 4 mPa·sec to 30 mPa·sec. If the viscosity value is higher than this, droplets cannot be ejected, and conversely, if the viscosity value is lower than this, the amount of droplet ejection is not stable. In addition, the temperature inside the head varies depending on the stability of the ink composition used, but it is preferable to use it at room temperature of 20°C to 45°C. Among these, in order to increase the solid content in the ink composition to improve film thickness and to achieve a viscosity that allows for stable ejection, a temperature of about 35°C to 40°C is generally adopted.

[0068] The characteristics of the composition as described above are primarily controlled by the solvent or surfactant constituting it, and in order to suppress drying of the composition in the nozzle portion during continuous printing, the solvent may be mainly one with a boiling point of 180°C or higher, and this solvent with a boiling point of 180°C or higher may be used alone or in multiple types, comprising 60% or more, preferably 80% or more, of the total solvent components. As solvents with a boiling point of 180°C or higher, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monoalkyl ether acetates such as diethylene glycol mono-n-butyl ether acetate; and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, high-boiling point solvents such as γ-butyrolactone, etc. may be used.

[0069] Examples of the composition ratio of solids in the black resin composition of the present invention when used in an inkjet method are as follows: (A) the curable resin and / or curable monomer is in the range of 25 to 60 mass%, (B) the black light-shielding particles in the component is in the range of 35 to 70 mass%, and (C) the color-adjusting particles in the component is in the range of 1 to 14 mass%; and more preferably, (A) the component is in the range of 35 to 55 mass%, (B) the black light-shielding particles are in the range of 40 to 60 mass%, and (C) the color-adjusting particles are in the range of 1 to 12 mass%. In addition, for example, when a resin (A-1) having an ethylenically unsaturated double bond and a monomer (A-2) having an ethylenically unsaturated double bond are used in combination as component (A), it is preferable that (A-1) / (A-2) be in the range of 10 / 90 to 90 / 10, and in the range of 30 / 70 to 70 / 30. In addition, when (A-1) and (A-2) are used in combination, an epoxy resin having two or more epoxy groups may be further used in combination to adjust the surface hardness or mechanical properties of the cured product. In this case, it is preferable to use the epoxy resin in the range of 1 to 60 parts by mass per 100 parts by mass of [(A-1)+(A-2)], and in the range of 10 to 50 parts by mass is more preferable.

[0070] Meanwhile, in the photolithography method, component (A) is a photocurable resin or a photocurable monomer, and an alkali-soluble resin for dissolving in an alkaline developer is mixed. Additionally, an alkali-soluble resin containing unsaturated groups having acidic groups such as polymerizable unsaturated groups and carboxyl groups within the molecule is preferably used. For example, a wide range of resins can be used, including an alkali-soluble resin containing unsaturated groups obtained by reacting a compound having polymerizable unsaturated groups and epoxy groups in one molecule, such as glycidyl meth)acrylate, with a portion of the carboxyl groups of a resin obtained by radical copolymerization of (meth)acrylic acid and a (meth)acrylic acid ester compound.

[0071] The curing method and curable resin component (A) of the light-blocking film formed on the transparent substrate are selected to be suitable for the heat resistance of the transparent substrate, the environment in which it is used, the required dimensional precision, and reliability.

[0072] Regarding the color and chromaticity of the black cured product (light-blocking film) obtained in this way, for the purpose of adjusting the black to an achromatic or bluish black, b in the CIE Lab color space display system * The value is -1.0 * <0.2, more preferably -1.0 * It is necessary to adjust to <0.0. In addition, this b in the present invention * The value is measured at a viewing angle of 2° or 10° using a D65 light source [standard illuminant of the main light of JIS Z8720 (light for color measurement)] or a C light source (auxiliary illuminant of the main light of JIS Z8720) used when displaying the object color illuminated by main light from the side opposite to the coated surface of the light-shielding substrate obtained above.

[0073] ​​To explain more specifically an example of an embodiment regarding the black photosensitive resin composition for use in a photolithography method with respect to the black resin composition for a light-shielding film of the present invention, the black photosensitive resin composition contains the above-described components (A) to (E) as main components. In this black photosensitive resin composition, preferably, among the solids excluding (D) solvent (including polymerizable monomer components that become solids after photocuring), (A-1) is a polymerizable unsaturated group-containing alkali-soluble resin in an amount of 10 to 60 mass%, (A-2) is a photopolymerizable monomer in an amount of 10 to 60 mass parts per 100 mass parts of (A-1), and (E) is a photopolymerization initiator in an amount of 2 to 50 mass parts per 100 mass parts of the total amount of (A-1) and (A-2). More preferably, (A-2) is 15 to 35 parts by mass with respect to 100 parts by mass of (A-1), and (E) is 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A-1) and (A-2). In addition, regarding the black light-blocking particles in component (B), the content is preferably in the range of 30 to 60 mass% with respect to the solid content excluding the solvent (D), and more preferably in the range of 40 to 50 mass%. In addition, regarding the color-adjusting particles in component (C), it is preferably in the range of 1 to 15 mass% with respect to the solid content excluding the solvent (D), and more preferably in the range of 2 to 7 mass%.

[0074] A method for forming a cured film using the black photosensitive resin composition of the present invention may be a method using photolithography. As such a method, the black photosensitive resin composition is first applied to the surface of a substrate, then the solvent is dried (prebaked), and then the resulting film is irradiated with ultraviolet rays through a photomask to cure the exposed portions, and a pattern is formed by performing a development process to elute the unexposed portions using an alkaline aqueous solution, and then heat curing (postbaking) is performed. Here, glass, a transparent film (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) is used as the substrate on which the black photosensitive resin composition is applied.

[0075] As a method for applying a black photosensitive resin composition to a substrate, in addition to known solution immersion and spray methods, any one of the following methods may be employed: using a roller coater, a land coater, a slit coater, or a spinner. By these methods, a coating film is formed by applying the composition to a desired thickness and then removing the solvent (pre-baking). After pre-baking, the solvent is removed by vacuum drying (VCD) at 20 to 100 Pa for 15 to 60 seconds, and then heated using an oven, a hot plate, etc. The heating temperature and heating time during this pre-baking are appropriately selected depending on the solvent used, and for example, it is performed at a temperature of 60 to 110°C for 1 to 3 minutes.

[0076] The exposure performed after prebaking is carried out by an exposure machine, and the photosensitive resin and photosensitive monomer in the parts corresponding to the pattern are sensitized by exposure through a photomask. The exposure machine and its exposure irradiation conditions are appropriately selected, and the exposure is carried out using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far-ultraviolet lamp.

[0077] Alkaline development after exposure is performed for the purpose of removing the coating film from the unexposed parts, and a desired pattern is formed by this development. Suitable developers for this alkaline development include, for example, aqueous solutions of carbonates of alkali metals or alkaline earth metals, or aqueous solutions of hydroxides of alkali metals. However, it is particularly preferable to develop at a temperature of 23 to 27°C using a weakly alkaline aqueous solution containing 0.03 to 1 mass% of carbonates such as sodium carbonate or potassium carbonate, and fine images can be precisely formed using commercially available developers or ultrasonic cleaners.

[0078] After developing in this manner, heat treatment (post-baking) is performed at a temperature of 200 to 240°C for 20 to 60 minutes. This post-baking is performed for purposes such as increasing the adhesion between the patterned black film and the substrate. This is done by heating with an oven, a hot plate, etc. And, by this, a substrate with a light-shielding film attached is obtained.

[0079] Regarding the color and color intensity of the black cured product (light-blocking film) obtained in this way, for the purpose of adjusting the black to an achromatic or bluish black, b in the CIE Lab color space display system * The value is -1.0 * <0.2, more preferably -1.0 * It is necessary to adjust to <0.0. In addition, this b in the present invention * The value is measured using a D65 light source [standard illuminant of the main light according to JIS Z8720 (light for color measurement)] or a C light source (auxiliary illuminant of the main light according to JIS Z8720), which is used when displaying the object color illuminated by main light from the side opposite to the coated surface of the light-shielding substrate obtained above.

[0080] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these.

[0081] [Example]

[0082] Various evaluations in the following examples were performed as follows, unless otherwise specifically noted.

[0083] [Solid content concentration]

[0084] 1g of the resin solution obtained from the synthesis example described below was impregnated into a glass filter [mass: W0(g)] and weighed [W1(g)], and the mass [W2(g)] after heating at 160℃ for 2 hours was calculated from the following formula.

[0085] ​​Solid content concentration (mass%) = 100 × (W2 - W0) / (W1 - W0).

[0086] [Sanga]

[0087] The resin solution was dissolved in dioxane and titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator [product name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.].

[0088] [Molecular weight]

[0089] Gel permeation chromatography (GPC) [Tosoh Inc. product name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH5000 (1) [Tosoh Inc., temperature: 40℃, rate: 0.6 ml / min] was used for measurement, and the weight average molecular weight (Mw) was calculated as a value converted to standard polystyrene [Tosoh Inc. PS-oligomer kit].

[0090] [Measurement of Average Secondary Particle Diameter]

[0091] For the obtained black light-shielding particle-containing dispersion or color-adjusting particle-containing dispersion, the average secondary particle diameter obtained by the cumulant method was measured using a particle size analyzer of the dynamic light scattering method (Particle Size Analyzer FPAR-1000 manufactured by Otsuka Denshi Co., Ltd.). The light-shielding black particle-containing dispersion or the color-adjusting particle-containing dispersion was diluted so that the concentration of particles dispersed in propylene glycol monomethyl ether acetate was 0.1 to 0.5 mass% and prepared as a sample for measurement.

[0092] [Viscosity Measurement]

[0093] The viscosity of the black resin composition for the shading film was measured at 23°C using an E-type viscometer (Tokisan Co., RE80L).

[0094] [Measurement of Shading Level (OD Value)]

[0095] The OD meter was measured using an Otsuka Denshi OD meter with a glass substrate with a light-blocking film attached after post-baking.

[0096] [Measurement of film thickness]

[0097] The glass substrate with a light-blocking film attached after post-baking was measured using a stylus-type film thickness meter [manufactured by Tencol Co., Ltd.].

[0098] [Inkjet Ejection Stability Test]

[0099] A black resin composition for a light-blocking film was introduced into a Konica Minolta IJ piezo-driven inkjet head (14 pL / drop; KM512M), and after purging and cleaning the inkjet head discharge surface, the discharge status of the ink composition was continuously monitored for 30 minutes using a flight observation camera to observe whether there were any significant problems, such as droplets not being discharged or the flight path not being clearly vertical. In addition, during an intermittent discharge test (counting the number of non-discharge nozzles when discharged after leaving the inkjet head discharge surface for 30 minutes and re-discharging), it was observed whether the number of non-discharge nozzles out of a total of 512 nozzles was satisfactory (within 10).

[0100] [Evaluation of Phenomenon Characteristics]

[0101] A black resin composition for a light-blocking film was applied using a spin coater onto a glass substrate of 125 mm × 125 mm so that the film thickness after post-baking was 1.2 μm, and pre-baked at 80°C for 1 minute. After that, the exposure gap was adjusted to 80 μm, a negative-type photomask with line / space = 20 μm / 20 μm was placed on the dried film, and ultraviolet light of 100 mJ / cm² was irradiated from an ultra-high pressure mercury lamp with an I-line illuminance of 30 mW / cm² to perform a photocuring reaction of the photosensitive area. Next, the exposed plate was subjected to shower development at 23°C at a pressure of 1 kgf / ㎠ in a 0.05% aqueous potassium hydroxide solution, with the time at which a pattern was observed set as the development omission time (BT seconds). After developing for 20 seconds, a spray rinse at a pressure of 5 kgf / ㎠ was performed to remove the unexposed portion of the film and form a pixel pattern on a glass substrate. Subsequently, heat post-baking was performed at 230°C for 30 minutes using a hot air dryer. The evaluation items and methods for the obtained light-blocking films in each example and comparative example are as follows.

[0102] Pattern linearity and surface smoothness of the coating film: A 20㎛ line after post-baking was observed using a microscope and SEM, and if burr adhesion was observed, it was judged as defective, and if not, it was judged as good. In addition, if there was non-uniformity in the line film thickness due to coarse particles, the smoothness was judged as poor.

[0103] In addition, the abbreviations used in synthetic examples, etc. are as follows.

[0104] BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of general formula (I) in which A is fluorene 9,9-diyl and R1 to R4 are hydrogen.

[0105] BPDA : 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

[0106] THPA: 1,2,3,6-tetrahydrophthalic anhydride

[0107] TPP: Triphenylphosphine

[0108] PGMEA: Propylene glycol monomethyl ether acetate

[0109] BDGAC: Diethylene glycol monobutyl ether acetate

[0110] DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [Product name DPHA manufactured by Nippon Kayaku Co., Ltd.]

[0111] HDDA: 1,6-hexanediol diacrylate

[0112] [Synthesized Example 1]

[0113] 78.63 g (0.17 mol) of BPFE, 24.50 g (0.34 mol) of acrylic acid, 0.45 g of TPP, and 114 g of PGMEA were added to a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred for 12 hours under heating at 100–105°C to obtain the reaction product.

[0114] Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product and stirred for 6 hours under heating at 120–125°C to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A-1)-1. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (converted to solid content) was 103 mgKOH / g, and the Mw by G PC analysis was 2600.

[0115] [Preparation of Resin Solution: Component A Solution]

[0116] Resin solutions A1 and A2 containing the following (A) component were prepared.

[0117] (1) Resin solution A1 (for inkjet printing: thermosetting resin composition)

[0118] Resin solution A1 was prepared by mixing 82.9 parts by mass of BDGAC, 6.3 parts by mass of a polymerizable unsaturated group-containing alkali-soluble resin solution (A-1)-1, 3.2 parts by mass of a phenol novolak type epoxy resin [product name JER154 of Mitsubishi Chemical Corporation, epoxy equivalent 178, average number of functional groups in 1 molecule 3.0], 4.0 parts by mass of DPHA, 1.24 parts by mass of a 10% BDGAC diluted solution of BYKR (registered trademark)-333 of Big Chem Japan Co., Ltd., and 2.95 parts by mass of 3-ureidopropyltriethoxysilane [product name KBE-585 of Shin-Etsu Chemical Co., Ltd.].

[0119] (2) Resin solution A2 (for photolithography printing: exposure / thermosetting resin composition)

[0120] Resin solution A2 was prepared by mixing 78.7 parts by mass of PGMEA, 12.3 parts by mass of alkali-soluble resin solution (A-1)-1, 2.41 parts by mass of DPHA, 0.81 parts by mass of photopolymerization initiator OXE-02 (manufactured by BASF), 1.24 parts by mass of a 10% BDGAC diluted solution of BYKR (registered trademark)-333 manufactured by Big Chem Japan Co., Ltd., and 2.95 parts by mass of 3-ureidopropyltriethoxysilane [Shin-Etsu Kagaku Kogyo Co., Ltd., product name KBE-585].

[0121] [Preparation of dispersion containing black light-blocking particles: (B) component]

[0122] (1) Black light-blocking particle-containing dispersion B1 (for inkjet printing):

[0123] A carbon black concentration of 25 wt% and a polymer dispersant of 10 wt% were prepared in BDGAC and dispersed in a bead mill to obtain dispersion B1 containing black light-blocking particles. The average secondary particle diameter of the carbon black in the obtained dispersion was 96 nm.

[0124] (2) Black light-blocking particle-containing dispersion B2 (for photolithography printing):

[0125] A carbon black concentration of 25 wt% and a polymer dispersant of 10 wt% were prepared in PGMEA and dispersed in a bead mill to obtain dispersion B2 containing black light-blocking particles. The average secondary particle diameter of the carbon black in the obtained dispersion was 111 nm.

[0126] [Preparation of dispersion containing color-adjusting particles: (C) component]

[0127] Color-modifying particle-containing dispersions C1 to C4 were prepared using a bead mill with CI pigment yellow pigment PY139 and polymer dispersants PGMEA or BDGAC. The composition and characteristics of each dispersion are shown in Table 1.

[0128]

[0129] [Black resin composition for shading films and preparation of the shading film, and evaluation]

[0130] [Examples 1–2]

[0131] A light-shielding ink (black resin composition for light-shielding) was prepared by mixing 12.8 parts by mass of resin solution A1, 13.5 parts by mass of carbon black dispersion B1, 3.8 parts by mass of PY139 dispersion C1, and 0.5 parts by mass of silica dispersion S1 (NANOBYK-3605 manufactured by BYK), and performing pressure filtration with a 1 μm deep filter. The initial viscosity (at room temperature) of the prepared ink was 10.3 mPa·sec [measured by a Type E viscometer (Tokisan-kyo) at 23°C]. This light-shielding ink was applied onto alkali-free glass by spin coating with varying rotation speeds, dried at 90°C for 5 minutes, and post-baked at 230°C for 30 minutes to produce a glass substrate with a light-shielding film attached. Each, a film thickness of 1.1 μm was designated as the sample of Example 1, and a film thickness of 1.4 μm was designated as the sample of Example 2. Table 2 shows the composition of each sample, and Table 3 shows the evaluation results of each sample.

[0132] In addition, the measurement of the reflective optical characteristics in Table 3 was performed as follows.

[0133] [Measurement of Reflective Optical Properties]

[0134] Measurements were taken using a Konica Minolta colorimeter CM2600d with a D65 light source and a 10° field of view on the side opposite to the side where the light-shielding film was formed, using a glass substrate with a light-shielding film attached after post-baking.

[0135] [Comparative Example 1]

[0136] A light-shielding ink (black resin composition for light-shielding) was prepared by mixing in the mass parts shown in Table 2, in the same manner as in Example 1, except for the exclusion of the dispersion containing PY139. This light-shielding ink was applied onto alkali-free glass, dried at 90°C for 5 minutes, and post-baked at 230°C for 30 minutes to produce a glass substrate with a light-shielding film attached. The thickness of the prepared sample film was 1.3 μm. The results of the sample evaluation are shown in Table 3.

[0137] As shown in Table 3, in Examples 1 and 2, the substrate with the light-shielding film attached also exhibits a light-shielding degree of 3 or higher, and b * Regarding the value of -0.08, which is close to zero, in Comparative Example 1, b * It exceeded 0.2.

[0138] [Examples 3–4, Comparative Examples 2–3]

[0139] A light-shielding ink (black resin composition for a light-shielding film) was prepared with the composition ratio shown in Table 2 by changing the average secondary particle diameter of PY139 in the dispersion containing color-adjusting particles, except as in Example 1, and a light-shielding film was formed on alkali-free glass as in Example 1. The evaluation results are shown in Table 3.

[0140] If the average secondary particle diameter of PY139 is lower than the average secondary particle diameter of carbon black (96 nm), then -1.0 * Regarding <0.2, in the case of each comparative example where the average secondary particle diameter of PY139 exceeds the average secondary particle diameter of carbon black, b * ​The result exceeded 0.2.

[0141] [Examples 5-6]

[0142] A light-shielding ink (black resin composition for a light-shielding film) was prepared according to the composition ratios shown in Table 2 by varying the added mass of PY139 in the dispersion containing color-adjusting particles relative to the mass of carbon black particles, except as in Example 1, and a light-shielding film was formed on alkali-free glass as in Example 1. The evaluation results are shown in Table 3. In all cases, compared to Comparative Example 1, in which PY139 particles do not coexist, b * Shift to the negative side to -1.0 * It showed <0.2.

[0143] [Examples 7–9, Comparative Example 4]

[0144] Using a resin solution (A2) for photolithography printing, a light-blocking ink (black resin composition for a light-blocking film) was prepared with the composition shown in Table 2. The black resin composition for a light-blocking film was applied to a glass substrate of 125 mm × 125 mm using a spin coater so that the film thickness after post-baking was 1.0 to 1.3 μm, and pre-baked at 80°C for 1 minute. After that, the exposure gap was adjusted to 80 μm, a negative-type photomask with line / space = 20 μm / 20 μm was placed on the dried film, and a photocuring reaction of the photosensitive area was performed by irradiating ultraviolet light of 100 mJ / cm² from an ultra-high pressure mercury lamp with an I-line illuminance of 30 mW / cm². Next, the exposed plate was subjected to a shower development at 1 kgf / ㎠ pressure at 23°C in a 0.05% potassium hydroxide aqueous solution, the time at which a pattern was observed was set as the development omission time (BT seconds), and after 20 seconds of development, a spray water wash at 5 kgf / ㎠ pressure was performed to remove the unexposed portion of the film and form a pixel pattern on a glass substrate, and then heat post-baking was performed at 230°C for 30 minutes using a hot air dryer.

[0145] In a substrate with a light-shielding film attached containing PY139 particles, b​* -1.0 * Regarding the value <0.2, for a substrate with a light-shielding film attached that does not contain PY139, b * The result exceeded 0.2.

[0146] [Evaluation of Inkjet Ejection and Development Characteristics]

[0147] The black resin compositions for light-blocking films prepared in Examples 1 to 6 were introduced into a Konica Minolta IJ piezo-driven inkjet head (14 pL / drop; KM512M), and after purging and cleaning the inkjet head discharge surface, the discharge status of the ink composition was continuously monitored for 30 minutes using an emergency observation camera. No significant problems were observed, such as droplets not being discharged or the discharge trajectory not being clearly vertical. Furthermore, in an intermittent discharge test (counting the number of non-discharge nozzles when discharged after leaving the inkjet head discharge surface for 30 minutes and re-discharging), it was found that the number of non-discharge nozzles out of a total of 512 nozzles was 2 or less, and no problems were observed with the inkjet discharge performance.

[0148] In addition, the black resin compositions for light-blocking films prepared in Examples 7 to 9 were evaluated for their development characteristics (pattern linearity and smoothness of the film surface) by the method described above, and it was confirmed that none of them had problems with linearity and smoothness.

[0149]

[0150]

[0151] In addition, a black photosensitive resin composition for a light-shielding film for photolithography is presented along with its evaluation.

[0152] [Preparation of Black Photosensitive Resin Composition]

[0153] Black photosensitive resin compositions of Examples 10 to 12 and Comparative Examples 5 and 6 were prepared by formulating according to the compositions shown in Table 4. The components used in each composition are shown below.​

[0154] (A-1) Alkali-soluble resin solution: Polymerizable alkali-soluble resin solution containing unsaturated groups prepared in Synthesis Example 1 (A-1)-1

[0155] (A-2) Photopolymerizable monomer: DPHA

[0156] (B) Black light-blocking particle dispersion: Carbon black dispersion of 25 mass% carbon black, 6 mass% polymer dispersant, and PGMEA solvent

[0157] (C) Color-adjusting particle dispersion:

[0158] (C)-1: A yellow pigment dispersion of 15 mass% Y139 (average secondary particle diameter 108 nm), 9 mass% polymer dispersant, and PGMEA solvent.

[0159] (C)-2: A yellow pigment dispersion in PGMEA solvent containing 15 mass% Y139 (average secondary particle diameter 123 nm) and 9 mass% polymer dispersant.

[0160] (C)-3: A yellow pigment dispersion in PGMEA solvent containing 15 mass% Y139 (average secondary particle diameter 158 nm) and 9 mass% polymer dispersant.

[0161] (C)-4: Solvent Blue 45 (Blue dye: Powder)

[0162] (D) Solvent: Mixed solvent of PGMEA and cyclohexanone

[0163] (E) Photopolymerization initiator: 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethanol=O-acetyloxime (BASF trade name Ilgacure OXE02)

[0164] (F) Surfactant: 1% PGMEA solution

[0165] (G) Silane coupling agent

[0166]

[0167] [Evaluation of Reflective Color]

[0168] The black photosensitive resin compositions of Examples 10 to 12 and Comparative Examples 5 and 6 were spin-coated onto a glass plate (5 inch × 5 inch), dried on a hot plate at 90°C for 1 minute, and then post-baked at 230°C for 30 minutes. In this way, a black cured product with a thickness of 1.45 μm was obtained.

[0169] Reflectance color measurements were performed using a UH-4100 manufactured by Hitachi High-Technologies Co., Ltd. on a solid substrate of this black cured material. The light source was a C light source (2° field of view) or a D65 light source (10° field of view).

[0170]

[0171] In Comparative Example 5, the color intensity of the reflected color is shown using only black light-blocking particles; however, to achieve achromaticity, it is necessary to make a* and b* close to 0. In particular, when the reflected color deviates slightly from achromaticity, there is a need to make b* a negative value in situations where a blue-toned color is required rather than a brown-toned one. In this regard, in Examples 10 to 12, it was found that by adding yellow adjusting particles having a color intensity similar to that of the black light-blocking particles, b* could be moved to the negative side without significantly altering the a* of the reflected color. Furthermore, to change b* from black to a blue-toned color, -1.0 <b*<0.2의 범위로 제어하는 것이 바람직하고, 실시예 10∼12에서 본 발명에 의해 그것이 실현되는 것을 나타내고 있다. 또한, 특히 청색 계통의 색상으로 하기 위해서는 1.0<b*<0.0으로 조정하는 것이 보다 바람직하고, 흑색 차광성 입자와 색 조정용 입자의 평균 2차 입자지름을 제어함으로써 제어 가능한 것도 알 수 있다.

[0172] On the other hand, as in Comparative Example 6, if a blue dye having a color intensity opposite to that of the black light-blocking particles (dissolved in a solvent and not a particle in the composition) is added, conversely, the value of b* increases, causing the reflected color to move in the opposite direction to the achromatic direction, and it can be seen that it is impossible to obtain the desired achromatic or slightly blue-toned color.

[0173] Accordingly, it has been revealed that the reflective color of a black cured product can be neutralized or adjusted to a desired color simply by selecting black light-blocking particles and color-adjusting particles of the same color family as in the present invention and adding a small amount.

Claims

Claim 1 (A) a resin curable by light or heat, and / or a monomer curable by light or heat; (B) a dispersion containing black light-shielding particles formed by dispersing black light-shielding particles in a dispersion medium; (C) a dispersion containing color-adjusting particles formed by dispersing color-adjusting particles in a dispersion medium; and (F) a black resin composition for a light-shielding film containing silica as an essential component, wherein the color-adjusting particles are organic pigments having a color intensity of the same color as the black light-shielding particles, and the average secondary particle diameter (D) of the black light-shielding particles in component (B). B ) is 60 nm to 150 nm, and the average secondary particle diameter (D) of the color-adjusting particles in component C is C ) is 60–150 nm, and (C) the average secondary particle diameter of the color-adjusting particles in the component (D C Average secondary particle diameter of black light-blocking particles in ) and (B) components (D B The ratio of ) (D C / D B ) is in the range of 0.2 to 1.2, and the average secondary particle diameter (D) of the color-adjusting particles in component (C) C The average secondary particle diameter (D) of the black light-shielding particles in component (B) B A black resin composition for a light-shielding film characterized by being smaller than ) and having a film thickness of 1.0 to 1.4 μm of the light-shielding film obtained by the black resin composition for a light-shielding film. Claim 2 In claim 1, the mass (m) of the color-adjusting particles included in component (C) C The mass of black light-blocking particles included in ) and component (B) (m B The ratio of )(m C / m B A black resin composition for a light-shielding film characterized by having a range of 0.03 to 0.

2. Claim 3 delete Claim 4 A black resin composition for a light-shielding film according to claim 1, characterized in that the black light-shielding particles are carbon black. Claim 5 A black resin composition for a light-shielding film according to claim 1, characterized in that the color-adjusting particles are CI Pigment Yellow 139, which is a yellow pigment, and / or CI Pigment Orange 61, which is an orange pigment. Claim 6 A black resin composition for a light-shielding film according to claim 1, wherein as components (A) a polymerizable unsaturated group-containing alkali-soluble resin and (A-2) a polymerizable monomer having an ethylenically unsaturated double bond are used, and further comprising (D) a solvent and (E) a photopolymerization initiator, wherein in the solid content containing the (A-2) polymerizable monomer that becomes solid after photocuring, (A-1) a polymerizable unsaturated group-containing alkali-soluble resin is 10 to 60 mass%, (A-2) a polymerizable monomer having an ethylenically unsaturated double bond is 10 to 60 mass parts per 100 mass parts of (A-1) a polymerizable unsaturated group-containing alkali-soluble resin, and (E) a photopolymerization initiator is 2 to 50 mass parts per 100 mass parts of the total amount of (A-1) a polymerizable unsaturated group-containing alkali-soluble resin and (A-2) a polymerizable monomer having an ethylenically unsaturated double bond, and further A black resin composition for a light-blocking film characterized in that the black light-blocking particles in component (B) of the solid content are 30 to 60 mass%, and the color-adjusting particles in component (C) of the solid content are 1 to 15 mass%. Claim 7 A black resin composition for a light-shielding film according to claim 6, characterized in that (A-1) a polymerizable alkali-soluble resin containing an unsaturated group obtained by reacting (a) a dicarboxylic acid or a tricarboxylic acid or its acid anhydride and (b) a tetracarboxylic acid or its acid dihydride with a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and a monocarboxylic acid containing an unsaturated group as a polymerizable alkali-soluble resin containing an unsaturated group. Claim 8 A light-shielding substrate obtained by applying and curing a black resin composition for a light-shielding film described in any one of claims 1, 2, and 4 to 7 onto one side of a transparent substrate, and b of the light-shielding substrate in the CIE Lab color space display system measured from the side opposite to the side of the transparent substrate where the light-shielding film is applied. * The value is -1.0 * A light-shielding substrate characterized by satisfying <+0.2.​ Claim 9 A color filter characterized by having a light-shielding substrate as described in claim 8. Claim 10 A touch panel characterized by having a light-shielding substrate as described in claim 8.

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