TW201535050A - Black resin composition for light shielding film, substrate with light shielding film color filter and touch panel - Google Patents

Abstract

This invention provides a black resin composition for a light shielding film for the purpose of obtaining a black cured film (light shielding film) from which reflected colors having a hue of colorless black or black with blueness from neutral color, a substrate with the light shielding film formed with the light shielding film on the transparent substrate, a color filter and a touch panel. This invention is a black resin composition for the light shielding film including the following component as essential components: (A) a curable resin cured by light or heat, and/or a curable monomer cured by light or heat, (B) a black light shelding particles-containing dispersing liquid formed by dispersing the black light shelding particles in a dispersion medium, and (C) a color modifing particles-containing dispersing liquid formed by dispersing the color modifing particles in a dispersion medium.

Description

Black resin composition for light-shielding film, substrate with light-shielding film, color Filters and touch panels

The present invention relates to a black resin composition for a light-shielding film, a light-shielding substrate including a light-shielding film obtained by curing the composition on a transparent substrate such as glass, and a liquid crystal display having the light-shielding substrate as a constituent element. A color filter for a display such as a liquid crystal display (LCD) or a touch panel for a display device. More specifically, it relates to a black resin composition which is hardened by light or heat to form a fine light-shielding film on a transparent substrate, and a light-shielding substrate which forms the light-shielding film at a selected position.

Color liquid crystal panels are used in various fields such as liquid crystal televisions, liquid crystal displays, and color liquid crystal mobile phones. The color liquid crystal panel has a structure in which a substrate on which a color filter is formed is bonded to a counter substrate (Thin Film Transistor (TFT) substrate) via a sealing material, and a liquid crystal is filled between the two substrates. Wherein, the method for manufacturing a color filter generally uses a method of forming a black matrix on a surface of a transparent substrate such as a glass or a plastic sheet (the black matrix is used by The color mixture between the red, green, and blue colors is suppressed to enhance the contrast. Then, a color pattern such as a stripe or a mosaic is sequentially used to form different hue of red, green, and blue which exhibit the function of all natural colors. Further, in the case where the touch panel circuit is formed on the front glass in the touch panel, in order to hide the wiring such as metal, a method of forming a light shielding layer formed in a frame shape at the peripheral portion of the screen is employed.

As a black matrix or a touch panel border forming a color filter The light-shielding material of the light-shielding film mainly uses carbon black having high light-shielding property. However, there is a problem that the reflected light of the carbon black usually does not become black which is not colored, that is, achromatic black, and in many cases, it is colored to a brown color tone, and thus the colored light is leaked. That is, light that is deviated from achromatic color, so that when a color filter is used to display black or a low-luminance color, the desired color cannot be displayed. Moreover, there is a problem that when the power is turned off (OFF), color deviation occurs with the black recessed groove (the frame portion around the display screen of the liquid crystal display device or the touch panel), resulting in poor design, in design In the diversification of demand, the demand for adjusting the hue of black is gradually increasing. Further, in the black light-shielding material other than carbon black, in many cases, it is not an achromatic black color, and therefore a technique of adjusting to an achromatic black color is required. In recent years, in order to improve the visibility of a liquid crystal panel and design thereof, it is required that the black matrix be "neutral black" (black which is not colored: achromatic). Moreover, in the touch panel, there is also a case where the color of the frame portion and the black groove are required to be matched. In this case, the touch panel frame is required to be neutral black.

In order to realize neutral black, Patent Document 1 describes that it is necessary to make a C light source Or the XYZ color system of the transmitted light and/or reflected light of the resin black matrix in the F10 light source The chromaticity coordinates in the system are consistent with the chromaticity coordinates of the source. Among them, the specifically described technique is to make carbon black and an organic pigment (the hue of the brown color which is deviated from the achromatic color with respect to the carbon black band, and the organic pigment contains a blue or purple color which is a complementary color of the brown color hue. The technique of dispersing and adjusting the chromaticity of the pigment requires the addition of more pigments for complementary colors. However, in particular, when the content of carbon black is high in the resist in order to improve the light-shielding property, if a pigment for a complementary color is further added in a large amount, it contributes to the formulation of a curable adhesive resin or a curable monomer component. When the ratio is relatively small, the coating film becomes difficult to be sufficiently cured, and the adhesion between the coating film and the glass substrate is lowered, and there is a problem that peeling or the like is likely to occur, or the electrical resistivity and adhesion after the environmental test are lowered. Adverse effects of the characteristics. Further, only the chromaticity adjustment of the transmitted light is described, but the chromaticity adjustment of the reflected light is not specifically shown.

In addition, as a method of making the reflected color neutral black, a technique of performing coloring by adding a red pigment or a yellow pigment of a coloring pigment to carbon black or titanium nitride as a light-shielding material is disclosed (Patent Document 2 and Patent Document 3) However, there is no mention of the state of dispersion of the light-shielding material and the coloring pigment used, and the technique of being able to positively adjust to the target neutral black or to have a preferred tendency to slightly change the color of the blue from the neutral black. The request is getting higher.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] WO95/35525 Specification

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-227467

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2014-119640

The present invention has been made in view of many disadvantages of the present invention, and an object thereof is to provide a light-shielding film which is a black light-shielding film having high light-shielding property and a black light whose color is adjusted to be achromatic, and a light-shielding film. Or a black chromatic color filter with a blue tint is a light-shielding film such as a black matrix. That is, one of the purposes is to obtain a chromaticity coordinate (a ^* , in the L ^* a ^* b ^* color system of the reflected light using a specific black light resin composition for dispersing the light-shielding material in the resin. b ^* ) 遮光 (0.0, 0.0) of the light-shielding film, practically, it is important to perform chromaticity adjustment for matching the chromaticity with the black groove, so that the purpose is to obtain a ^* , b ^* A light-shielding film whose chromaticity is adjusted to the - side (negative side) to match the hue of a black groove or the like.

In order to solve the problems of the prior art, the inventors of the present invention have conducted intensive studies, and as a result, it has been found that a specific one is used in addition to black light-blocking particles such as carbon black and titanium black, and a curable resin or a curable monomer. The color adjustment particles are used to form a black resin composition, and the chromaticity of the light-shielding film can be adjusted to be achromatic or blue-black. Further, in the black resin composition, the ratio of the average secondary particle diameter of the black light-shielding particles to the average secondary particle diameter of the color-adjusting particles is set to a specific range, and the quality of the black light-shielding particles is obtained. The mass ratio of the mass of the particles for color adjustment is set to a specific range, and the adjustment of the chromaticity can be surely achieved. this In the case of the hue of the color-adjusting particles, it is found that when the carbon black is a hue which is deviated from the achromatic color to the brown color, the blue or purple pigment which is in a complementary color (opposite color) relationship with the discolored hue is not disposed. Conversely, it contains a small amount of yellow or orange pigment in the same color as the deviated hue, thereby maintaining film properties or reliability after hardening, and adjusting the chromaticity of the light-shielding film to achromatic or bluish-toned Black to complete the present invention.

That is, the gist of the present invention is as follows. that is,

(1) The present invention relates to a black resin composition for a light-shielding film comprising the following components as an essential component: (A) a curable resin using light or heat, and/or a curable monomer using light or heat, (B) A dispersion liquid containing black light-blocking particles obtained by dispersing black light-shielding particles in a dispersion medium, and (C) a dispersion liquid containing color adjustment particles obtained by dispersing color adjustment particles in a dispersion medium.

(2) The black resin composition for a light-shielding film according to (1), wherein the average secondary particle diameter D _C of the color-adjusting particles in the component (C) and the black light-shielding particles in the component (B) The ratio D _C /D _B of the average secondary particle diameter D _{B is} in the range of 0.2 to 1.2, and the color m _C of the color-adjusting particles contained in the component (C) and the black light-shielding property contained in the component (B) The ratio m _C /m _B of the mass m _B of the particles is in the range of 0.03 to 0.2.

(3) The black resin composition for a light-shielding film according to (1) or (2), wherein the black light-shielding particles are carbon black particles.

(4) The black resin composition for a light-shielding film according to any one of (1) to (3), wherein the color-adjusting particles are C.I. pigments as yellow pigments Yellow 139 and/or C.I. Pigment Orange 61 as an orange pigment.

(5) The present invention is also a black resin composition for a light-shielding film, which is characterized by In the black resin composition for a light-shielding film, an alkali-soluble resin containing a polymerizable unsaturated group and a polymerizable monomer having an ethylenically unsaturated double bond are used as the component (A), and further contains (D) a solvent. And (E) a black resin composition for a light-shielding film according to any one of (1) to (4), and a solid component of a polymerizable monomer which is solid after being photocured, The alkali-soluble resin containing a polymerizable unsaturated group is 10% by mass to 60% by mass, and the polymerizable monomer having an ethylenically unsaturated double bond is 100 parts by mass of the alkali-soluble resin containing a polymerizable unsaturated group. 10 parts by mass to 60 parts by mass, and (E) is 2 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin containing a polymerizable unsaturated group and a polymerizable monomer having an ethylenically unsaturated double bond. 50 parts by mass, further, the black light-shielding particles in the component (B) are 30% by mass to 60% by mass, and the color-adjusting particles in the solid component (C) are 1% by mass to 15% by mass. %.

(6) The black resin composition for a light-shielding film according to (5), wherein the alkali-soluble resin containing a polymerizable unsaturated group is used to (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) A polymerizable unsaturated group obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof with a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid containing an unsaturated group Alkali soluble resin.

(7) The substrate with a light-shielding film, wherein the light-shielding film is coated with a black resin composition according to any one of (1) to (6) a light-shielding film obtained by curing a single surface on a transparent substrate, and a light-shielding film in a CIE Lab color space system measured from the opposite side of the surface of the transparent substrate on which the light-shielding film is applied The b ^* value of the substrate satisfies -1.0 <b ^* <+0.2.

(8) The present invention is also a color filter comprising the substrate with a light shielding film according to (7).

(9) The present invention is also a touch panel characterized by comprising the substrate with a light shielding film according to (7).

By using the black resin composition of the present invention, a black cured film (light-shielding film) which controls the color of the reflection color to be achromatic black or the color of the black color with a blue tone from achromatic color can be formed on the transparent substrate, and can be formed. The transparent substrate with a light shielding film having the light shielding film is applied to a color filter or a touch panel for a display device. That is, according to the present invention, it is possible to design a color filter or a touch panel which is excellent in design even when the display screen is not lit.

Hereinafter, the present invention will be described in detail.

The use of light or heat as the component (A) in the black resin composition of the present invention The curable resin and/or the curable monomer which utilizes light or heat is a functional group (for example, (meth) acrylonitrile group, vinyl group, etc. which have at least one or more hardening reaction by heat or light in a molecule. A resin or a monomer having a group having an ethylenically unsaturated double bond or a cyclic reactive group such as an epoxy group or an oxetanyl group can be used.

a compound having an ethylenically unsaturated double bond as the component (A) (A-1) a resin having an ethylenically unsaturated double bond and (A-2) a polymerizable monomer having an ethylenically unsaturated double bond, which is hardened by light or heat in consideration of processing conditions such as coating. The conditions, the physical properties of the cured product, and the like may be used alone (A-1) or (A-2), or may be used in combination at any ratio.

The component (A-1) is, for example, one or more having a carboxyl group. 3 to 5 kinds of polymerizable monomers of monomers (the monomers are selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and A An alkyl acrylate or an alkyl methacrylate such as butyl acrylate (hereinafter, these compounds may be collectively described as "alkyl (meth) acrylate"), and a cyclic (meth) acrylate ring a carboxyl group of a copolymer synthesized by an ester, hydroxyethyl (meth)acrylate, styrene or the like, and a glycidyl methacrylate having an epoxy group or an isocyanate group and at least one or more ethylenically unsaturated double bonds; A curable resin having an unsaturated double bond which is cured by light or heat obtained by reaction of isocyanate ethyl acrylate or methacryl oxime isocyanate. From the viewpoint of heat resistance and developability, a curable resin having such a structure is preferably a curable resin having a weight average molecular weight of 5,000 to 100,000 and an acid value of 50 to 150.

Further, as another example of the component (A-1), a bisphenol A type epoxy resin may be mentioned. Bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, trisphenol methane ring An epoxy (meth) acrylate type curable resin obtained by reacting an epoxy resin such as an oxygen resin or a dihydroxybenzene type epoxy resin with (meth)acrylic acid. The epoxy (meth) acrylate acid addition product obtained by further reacting the epoxy (meth) acrylate type curable resin with an acid monoanhydride and an acid dianhydride can be made alkaline by photolithography. A case where the developed pattern-forming resin composition is suitably used. In this case, a suitable weight average molecular weight is from 2,000 to 20,000, and an acid value of from 50 to 150.

As a preferred example in the case where the present invention is used in the photolithography method An epoxy (meth) acrylate acid adduct obtained by further reacting the epoxy (meth) acrylate type curable resin with an acid monoanhydride and an acid dianhydride to make (a) a dicarboxylic acid or Reaction of a tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof, and an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid containing an unsaturated group An alkali-soluble resin obtained by carrying out the reaction. Here, the molar ratio of (a)/(b) is preferably 0.01 to 10.

a bisphenol which is a raw material of the epoxy (meth) acrylate acid adduct Examples include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, and bis ( 4-hydroxyphenyl)indole, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxybenzene) Dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, 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-dual (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)anthracene, 9,9-bis(4-hydroxy-3) -Methylphenyl)anthracene, 9,9-bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis ( 4-hydroxy-3-fluorophenyl)indole, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichloro Phenyl) ruthenium, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, 4,4'-biphenol, 3,3'-biphenol, and the like, and derivatives thereof. Among these, a compound having a fluoren-9,9-diyl group is particularly suitably used.

Secondly, the bisphenols are reacted with epichlorohydrin to obtain two shrinkages. A glyceryl ether based epoxy compound. At the time of this reaction, oligomerization of the diglycidyl ether compound is generally accompanied, and thus an epoxy compound of the following formula (I) is obtained.

In the formula (I), R ₁ , R ₂ , R ₃ and R ₄ 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-, - SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 芴-9,9-diyl or directly Bonding. l is a number from 0 to 10. Preferred R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, and preferred A is a fluoren-9,9-diyl group. Further, since l usually has a plurality of values mixed, the average value is 0 to 10 (not limited to an integer), and the average value of the preferred l is 0 to 3. When the value of l exceeds the upper limit, when the black resin composition using an alkali-soluble resin (the alkali-soluble resin is synthesized using the epoxy compound) is used, the viscosity of the composition becomes too large and becomes too large. When the coating is performed well, the alkali solubility is not sufficiently provided, and the alkali developability is extremely poor.

Secondly, the compound of the formula (I) is used as a single group containing an unsaturated group. Acrylic acid or methacrylic acid of a carboxylic acid or a reactant having a hydroxyl group obtained by reacting these two compounds with (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof The reaction is carried out in a range in which the molar ratio of (a)/(b) is preferably 0.01 to 10, and a structure having an epoxy (meth) acrylate acid adduct structure represented by the following formula (II) is obtained. A polymer-soluble unsaturated alkali-soluble resin.

(wherein R ₁ , R ₂ , R ₃ , R ₄ and A are the same definitions as in the formula (I), R ₅ represents a hydrogen atom or a methyl group, and X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ 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 to 2), and n represents a number of 1 to 20 )

The epoxy (meth) acrylate acid adduct (II) is an alkali-soluble resin containing a polymerizable unsaturated group having both an ethylenically unsaturated double bond and a carboxyl group, and thus is used as an alkaline development type photo lithography. In the case of using the black resin composition of the present invention, (A-1), excellent photocurability, good developability, and patterning properties are imparted, and a favorable pattern shape is obtained.

The (a) dicarboxylic acid or tricarboxylic acid or an anhydride thereof used in the epoxy (meth) acrylate acid adduct of the formula (II) uses a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid or an anhydride thereof or An alicyclic dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an anhydride thereof. Here, the chain hydrocarbon dicarboxylic acid or the tricarboxylic acid or its anhydride is, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, sebacic acid, cis malic acid, and c. a compound such as diacid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid or diglycolic acid, or a dicarboxylic acid further introduced with any substituent Or a tricarboxylic acid or an anhydride thereof. Further, the alicyclic dicarboxylic acid or the tricarboxylic acid or an anhydride thereof is, for example, a cyclobutanedicarboxylic acid, a cyclopentanedicarboxylic acid, a hexahydrophthalic acid, a tetrahydrophthalic acid, a norbornane II. The compound such as a carboxylic acid may be a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof to which an optional substituent is further introduced. Further, the aromatic dicarboxylic acid or the tricarboxylic acid or an acid anhydride thereof may be, for example, a compound such as phthalic acid, isophthalic acid or trimellitic acid, or a dicarboxylic acid or further substituted with an optional substituent. Tricarboxylic acid or its anhydride.

Further, in the epoxy (meth) acrylate acid addition of the formula (II) The (b) tetracarboxylic acid or its acid dianhydride may be a chain hydrocarbon tetracarboxylic acid or an acid dianhydride or an alicyclic tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polycarboxylic acid or an acid dianhydride thereof. . Here, the chain hydrocarbon tetracarboxylic acid or its acid dianhydride may be, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or the like, or may be a tetracarboxylic acid or a further substituted group thereof. Acid dianhydride. Further, the alicyclic tetracarboxylic acid or the acid dianhydride thereof is, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, or the like. Further, it may be a tetracarboxylic acid or an acid dianhydride thereof to which a substituent is further introduced. Further, examples of the aromatic tetracarboxylic acid or the acid dianhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid or acid dianhydride thereof, and further may be further A tetracarboxylic acid having a substituent or an acid dianhydride thereof is introduced.

Used in the epoxy (meth) acrylate acid addition of the formula (II) The molar ratio (a)/(b) of (a) the dicarboxylic acid or the tricarboxylic acid or its anhydride to (b) the tetracarboxylic acid or the acid dianhydride thereof is preferably 0.01 to 10, more preferably 0.1 to 3.0. . If the molar ratio (a)/(b) deviates from the above range, an optimum molecular weight cannot be obtained, and in the black resin composition used as (A-1), alkali developability, heat resistance, solvent resistance Since the pattern shape or the like is deteriorated, it is not preferable. Further, as the molar ratio (a)/(b) is smaller, the molecular weight is larger, and the alkali solubility tends to be deteriorated.

Moreover, the weight of the epoxy (meth) acrylate acid adduct of the formula (II) The amount average molecular weight (Mw) is preferably between 2,000 and 10,000, particularly preferably between 3,000 and 7,000. If the weight average molecular weight (Mw) is less than 2,000, the black resin composition used as (A-1) cannot maintain the pattern adhesion during development, causing pattern peeling, and if the weight average molecular weight (Mw) exceeds 10,000, Then, it becomes easy to leave a development residue or a residual film of an unexposed part. Further, it is desirable that the acid value thereof is in the range of 30 mgKOH/g to 200 mgKOH/g. When the value is less than 30 mgKOH/g, the alkali development of the black resin composition used as (A-1) tends to be deteriorated, and therefore special development conditions such as a strong alkali are required. On the other hand, when it exceeds 200 mgKOH/g, the penetration of the alkaline developing solution into the black resin composition used as (A-1) becomes too fast, and peeling development occurs, which is not preferable.

Epoxy (meth) acrylate acid of the formula (II) utilized in the present invention The adduct can be produced by the known method (for example, the method described in JP-A-H08-278629 or JP-A-2008-9401). First, a method of reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the formula (I) is, for example, a method of adding a monocarboxylic acid containing an unsaturated group such as an epoxy group of an epoxy compound. In a solvent, in the presence of a catalyst (such as triethylbenzylammonium chloride or 2,6-diisobutylphenol), the mixture is heated and stirred at 90 to 120 ° C while being blown into the air. The method of reaction. Next, as a method of reacting an acid anhydride with a hydroxyl group of a reaction product epoxy acrylate compound, a predetermined amount of an epoxy acrylate compound and an acid dianhydride and an acid monoanhydride is added to a solvent in a catalyst (tetraethyl bromide). A method of heating and stirring at 90 ° C to 130 ° C in the presence of ammonium chloride or triphenylphosphine to cause a reaction.

Further, (A-2) a polymerizable monomer (photopolymer or photopolymerizable monomer) having an ethylenically unsaturated double bond may, for example, be 2-hydroxyethyl (meth)acrylate or (meth)acrylic acid- a (meth) acrylate having a hydroxyl group such as 2-hydroxypropyl ester or 2-hydroxyhexyl (meth)acrylate, or ethylene glycol di(meth)acrylate or diethylene glycol di(methyl) Propylene Acid ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylic acid Ester, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (methyl) (meth)acrylates such as alkylene oxide modified hexa(meth)acrylate of acrylate and phosphazene, and dipentaerythritol hexa(meth)acrylate modified by caprolactone, (A-2) can be used. One or two or more of these. Further, it is preferable that the polymerizable monomer having an ethylenically unsaturated double bond has three or more polymerizable groups and can be used as a light or thermosetting resin (in the case of photolithography, it contains a polymerizable unsaturated group). A monomer in which molecules of the base-based alkali-soluble resin are cross-linked to each other. Further, when the (A-2) polymerizable monomer having an ethylenically unsaturated double bond is used as a black resin composition used in the photolithography method, a compound which does not have a free carboxyl group is used.

Further, the component (A) may be exemplified by (A-3) having at least one molecule in the molecule. A compound having a cyclic reactive group such as an epoxy group or an oxetanyl group. Specific examples thereof include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol oxime type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, and a polyhydric alcohol. Glycidyl ether, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth)acrylate as a unit, 3,4-epoxycyclohexanecarboxylic acid-(3',4'-epoxy group An alicyclic epoxy compound represented by cyclohexyl)methyl ester, having a bicyclic ring A polyfunctional epoxy compound having a pentadiene skeleton (for example, HP7200 series manufactured by Dixon Co., Ltd.), 1,2-epoxy-4-(2,2-bis(hydroxymethyl)-1-butanol) 2-oxopropyl)cyclohexane adduct (for example, "EHPE 3150" manufactured by DAICEL Co., Ltd.), epoxidized polybutadiene (for example, Nisso (NISSO)-PB manufactured by Japan Soda Corporation) .JP-100"), an epoxy compound having an anthracene skeleton, and the like.

(A) component may have ethylene such as (A-1) and (A-2) The compound of the unsaturated double bond and (A-3) one of the compounds having a cyclic reactive group may be used in combination.

In addition, a compound having an ethylenically unsaturated double bond is used as (A) In the case of a component, a photopolymerization initiator, a thermal polymerization initiator, or the like which generates radicals, cations, anions or the like due to ultraviolet rays or heat is preferably used. Further, in the case of using (A-3) a compound having a cyclic reactive group, a compound which reacts with a cyclic reactive group due to light or heat (for example, a compound having a carboxyl group, an amine group, a hydroxyl group, or a thiol group) is preferably used. Etc.) used as a hardener.

It is preferred to select a compound having a refractive index of the cured product of the component (A) which is 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 a styrene monomer or the like having an aromatic group in a chemical structure. In the case of an epoxy resin, the refractive index is 1.50 to 1.60. If a bisphenol epoxy resin or an aromatic anhydride hardener is used, the refractive index becomes high; if an aliphatic epoxy resin or an alicyclic epoxy resin is used; Or an alicyclic acid anhydride hardener, the refractive index becomes relatively low.

In addition, as for the content of the component (A), it is only necessary to remove the solvent component. The solid content of the black resin composition (including the curable monomer component which becomes a solid component after hardening) may be in the range of 25% by mass to 60% by mass, and preferably in the range of 35% by mass to 55% by mass.

As the black light-shielding particles contained in the component (B), there is no special Black organic pigments, inorganic pigments, and the like are used in a limited manner. Examples of the black organic pigment include black, cyanine black, nigrosine, and mesaconamine. Examples of the inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, and titanium nitride. These black light-shielding particles may be used alone or in combination of two or more. From the viewpoint of the light blocking ratio of the target film and the storage stability of the composition for a light shielding film, a black pigment having a refractive index of more than 1.6 and absorbing visible light is mainly used. The black light-blocking particles used in the present invention are preferably carbon black. As the carbon black, any of lamp black, acetylene black, hot carbon black, channel black, and furnace black can be used. Further, in order to adjust the light-shielding property, one type of other light-shielding components such as a black dye or a plurality of kinds of light-shielding components may be used, and it is preferable that the black light-shielding particles are 60% or more of the light-shielding component. For example, when a light-shielding component of a quasi-black organic pigment system or a dye system is used in a large amount, the light-shielding ratio is lowered, and it becomes difficult to obtain a desired light-shielding ratio (OD).

These black light-shielding particles or other light-shielding components are dispersed in a bead mill together with a dispersion medium containing a dispersant such as a polymer dispersant and a solvent to prepare a dispersion liquid containing black light-shielding particles (including black light-shielding particles). The dispersion liquid) is mixed with the component (A) and the component (C) described later to prepare a black resin composition for a light-shielding film of the present invention. The average secondary particle diameter D _B of the black light-shielding particles dispersed in the dispersion is prepared to be 60 nm to 150 nm, preferably 80 nm to 120 nm. In the present invention, the "average secondary particle diameter" refers to a value obtained by a dynamic light scattering method and diluted by a dispersion solvent or a corresponding solvent, and the average particle diameter determined by the accumulation method. Further, the black light-shielding particles are in a form of a cluster of fine primary particles such as carbon black, and the particle diameter (average secondary particle diameter) in this form exhibits physical properties, and therefore is important; and even if it is not connected In the case of a cluster of grapes, the particles having a fine particle diameter (average primary particle diameter) are more likely to aggregate in the dispersion, and the particle diameter (average secondary particle diameter) in the aggregated state becomes important. Therefore, in the present invention, the particle diameter in the dispersion liquid is set to the average secondary particle diameter.

For example, in the case of carbon black, it is a value measured at a particle concentration of 0.1% by mass in a propylene glycol monomethyl ether acetate solvent. When the average secondary particle diameter D _{B is} less than 60 nm, it is necessary to add a polymer dispersing agent which is required to increase the concentration of the black light-blocking particles in order to achieve a high light-shielding ratio, and it is likely to cause an increase in viscosity during storage. When the average secondary particle diameter D _B exceeds 150 nm, the surface smoothness of the formed light-shielding film is not preferable, and the linearity of the pattern edge when formed by photolithography is impaired.

That is, the light-shielding film for the touch panel and the color filter are used in the black matrix. The opacity (OD=-log [transmission]) is required to be OD4 or more, and on the other hand, a film thickness of 3 μm or less, preferably 2 μm or less is required. The reason is: in the touch panel, the wire is prevented from being broken when the metal wire on the light shielding film of the touch panel is connected with the conductive film on the touch panel, and the color filter is flat in the black matrix. Chemical. In order to obtain a high degree of opacity even in such a thin light-shielding film, for example, it is preferable to set the carbon black-based black light-shielding particles with respect to all the solid components in the composition. 35 mass% or more and 70 mass% or less.

Examples of the yellow pigment and the orange pigment which can be used for the color-adjusting particles contained in the component (C) include CI Pigment Yellow (PY) 20, CI Pigment Yellow (PY) 24, and CI Pigment Yellow (PY) 31. CI Pigment Yellow (PY) 53, CI Pigment Yellow (PY) 83, CI Pigment Yellow (PY) 86, CI Pigment Yellow (PY) 93, CI Pigment Yellow (PY) 94, CI Pigment Yellow (PY) 109, CI Pigment Yellow (PY) 110, CI Pigment Yellow (PY) 117, CI Pigment Yellow (PY) 125, CI Pigment Yellow (PY) 137, CI Pigment Yellow (PY) 138, CI Pigment Yellow (PY) 139, CI Pigment Yellow ( PY) 147, CI Pigment Yellow (PY) 148, CI Pigment Yellow (PY) 150, CI Pigment Yellow (PY) 153, CI Pigment Yellow (PY) 154, CI Pigment Yellow (PY) 166, and CI Pigment Yellow (PY) 173, etc.; CI Pigment Orange (PO) 36, CI Pigment Orange (PO) 43, CI Pigment Orange (PO) 51, CI Pigment Orange (PO) 55, CI Pigment Orange (PO) 59, CI Pigment Orange (PO) 61 CI Pigment Orange (PO) 71, CI Pigment Orange (PO) 73, etc.; among them, CI Pigment Yellow can maintain the OD value at 4.0 or more, and can efficiently make the b ^* value negative, which is preferable. Further, a specific example of the particles for color adjustment which can be particularly preferably used is PY139 or PO61.

For example, when carbon black is used as the black light-shielding particles, the carbon black usually has a reflection color of a brown color, and therefore PY139 and PY150 of the same color pigment are preferable. If it is the same color, the black light-shielding particles are the hue from the achromatic color. In the case of chromaticity, the hue of the deviation is displayed. The color of the same color of chromaticity. For example, if the black shading particles are the hue that deviates from the brown color. Chroma, in the same position on the hue ring Orange, yellow hue. The chromaticity is the same color. That is, if it is the opposite color of the light-shielding material, the black light-shielding particles are the hue from the achromatic color. In the case of chromaticity, the hue of the deviation is displayed. The opposite color of chromaticity. For example, if the shading material is a hue that deviates from the brown color. Chromaticity, the blue and purple hue near the diagonal on the hue circle. The chromaticity is the opposite color. That is, the carbon black which is one of the black light-shielding particles is a hue which is deviated from the achromatic color to the brown color. On the other hand, it has been conventionally considered that the blue pigment of the pigment/dye which is complementary color (the opposite color) to the shifted hue is considered. / Dyes" or "Purple Pigments / Dyes".

These color adjustment particles are dispersed in a bead mill together with a dispersion medium containing a dispersant such as a polymer dispersant and a solvent to prepare a dispersion liquid (dispersion liquid containing particles for color adjustment) containing particles for color adjustment. The black resin composition for a light-shielding film of the present invention can be prepared by mixing the component (A) and the component (B). Further, with respect to the component (C) dispersed in the color adjusting average secondary particle diameter D _C of the particles, than the average secondary particle diameter D _B is reacted with the component (B), the light-shielding black particles D _C /D _B becomes a range of 0.2 to 1.2. The average secondary particle diameter D _C is a value obtained by a dynamic light scattering method and diluted by a dispersion solvent or a corresponding solvent, and the average particle diameter determined by the accumulation method.

For example, in the case of yellow pigment particles, the dispersion is a measured value of a particle concentration of 0.1% by mass to 1.0% by mass. If the ratio of the average secondary particle diameter D _C /D _B exceeds 1.2, the effect of making the b ^* value negative is substantially not found. Further, if the ratio of the average secondary particle diameter D _C /D _{B is} less than 0.2, the dispersion stability in the composition is lowered. Since the carbon black-containing dispersion liquid used in the use of the light-shielding film has an average secondary particle diameter D _B of 60 nm to 150 nm, it is difficult to prepare a dispersion containing a yellow pigment having a D _C of 30 nm or less. The preferred average secondary particle diameter of D _C is from 60 nm to 150 nm, and more preferably from 80 nm to 120 nm.

Furthermore, in the present invention, the mass m _C of the color-adjusting particles (solid content) contained in the component (C) and the black light-shielding particles (solid) contained in the component (B) are contained in the composition. The mass ratio m _C /m _B of the mass m _B of the component is in the range of 0.03 to 0.2. If the m _C /m _{B is} less than 0.03, the effect of reducing b ^* is not found; if it exceeds 0.2, the light blocking ratio (OD/μm) is lowered.

However, in the substrate with a light-shielding film in which the composition is a cured film, the mechanism by which the color-adjusting particles exhibit a function of reducing b ^* can be considered as follows. In other words, in the substrate with a light-shielding film, a part of the light incident from the transparent substrate side is mainly reflected and scattered by the particles dispersed in the light-shielding film at the interface between the transparent substrate and the transparent substrate, and is emitted from the transparent substrate side. The scattering of the microparticles occurs when the particle diameter thereof is lower than the wavelength of the light, and particularly in the Rayleigh scattering region, the wavelength dependence of the backscattering with respect to the direction in which the light is incident on the microparticles becomes remarkable. The backscattering caused by the yellow pigment or the orange pigment which is equal to or less than the particle diameter of the carbon black particles scatters more light in the blue region in the complementary color relationship to the rear.

In order to effectively exhibit the color adjustment of the above light-shielding film (the b ^{* is} adjusted to the negative side), it is necessary that the black light-shielding particles and the color-adjusting particles do not condense themselves in the film coated on the composition and the transparent substrate. The ground is stably dispersed. Therefore, the black light-shielding particles and the color-adjusting particles of the present invention are dispersed together with the polymer dispersant in an organic solvent by a bead mill, and supplied as a dispersion liquid.

In the black resin composition for a light-shielding film of the present invention, it is used for dissolution. The light-curable resin or the like and the black light-shielding particles or the color-adjusting particles are dispersed, and one or more types of (D) solvents may be contained, and are not particularly limited. Examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and terpenes such as α-terpineol or β-terpineol, acetone, methyl ethyl ketone, and ring. Ketones such as ketone 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol ethers such as diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl Acetate such as cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., can be prepared by dissolving and mixing using several kinds of these solvents. A uniform composition in which the light-shielding particles or the color-adjusting particles are stably dispersed.

The content of such a solvent is as long as it is relative to the black resin composition 100. The mass portion may be in the range of 5 parts by mass to 2000 parts by mass, preferably 50 parts by mass to 1000 parts by mass, and may be adjusted to an appropriate solid content and solution viscosity according to a method of coating on a transparent substrate. And use.

The black resin composition of the present invention is used as a photocurable composition (black When the photosensitive resin composition is applied to a photolithography method or the like, it is necessary to contain (E) a photopolymerization initiator. Examples of the (E) photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and dichloroacetophenone. Acetophenones such as trichloroacetophenone and p-tert-butylacetophenone, diphenyls such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone Ketones, benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(ortho Chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole , 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1, Halogenated methylthiazole compounds such as 3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl) -4,6-double (three Chloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-( 4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis (three Chloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three Halogenated methyl-s-triazine-based compounds such as azine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 1, 2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzhydrazide), 1-(4-phenylthiophenyl)butane-1,2- Diketo-2-indole-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-indole-O-acetate, 1-(4- O-mercapto lanthanide compounds such as methylthiophenyl)butan-1-one oxime-O-acetate, benzophenanthrene Sulfur compounds such as methyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-B Anthraquinones such as guanidine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylanthracene, azobisisobutylnitrile, benzammonium peroxide, peroxidation An organic peroxide such as an alkene, a thiol compound such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole; a tertiary amine such as triethanolamine or triethylamine. Among them, from the viewpoint of easily obtaining a high sensitivity black photosensitive resin composition, it is preferred to use an O-fluorenyl compound. Further, two or more kinds of these photopolymerization initiators can also be used. Further, the photopolymerization initiator in the present invention is used in the sense of containing a sensitizer.

Further, in the black resin composition for a light-shielding film of the present invention, Additives such as a hardening accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant are required. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butyl catechol, and phenothiazine. Examples of the antioxidant include hindered phenol compounds, and plasticizers. Examples of dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate include glass fibers, cerium oxide, mica, and alumina. Examples of antifoaming agents or leveling agents include hydrazine. A ketone system, a fluorine system or an acrylic compound. Further, examples of the surfactant include a fluorine-based surfactant, an anthrone-based surfactant, and the like.

In addition, it is black design which is blue with blue color In a light-shielding film or the like of a display device such as an LCD or a touch panel, there is a demand for increasing the design property by setting the reflectance of the light-shielding film to an appropriate range. For this purpose, inorganic particles such as cerium oxide can be used as an additive in the composition of the present invention.

Method for coating a light-shielding film with a black resin composition on a transparent substrate In addition to the known solution dipping method and spraying method, any method such as an ink jet machine, a roll coater, a sand coater, a slit coater or a rotary machine can be employed. The solvent is adjusted to obtain a suitable viscosity of a favorable coating film, and after coating to a desired thickness by these methods, the solvent is removed (prebaked) under heating or reduced pressure to form a dried coating film. Then, it is hardened by light and/or heat, thereby preparing a target substrate with a light-shielding film.

A printing method for forming a light shielding film pattern on a transparent substrate exists in a light micro In the shadow method, the coating film obtained by applying the composition onto a transparent substrate and drying it is irradiated with ultraviolet rays, and the unexposed portion is removed by a developing solution, and further heat treatment is performed. Further, there are a method of printing using a transfer printing plate, such as a screen printing method, a gravure printing method, a gravure printing method, etc., and in recent years, the inkjet printing method has been received as a digital printing method without a mask or a printing plate. attention. The black resin composition for a light-shielding film of the present invention can be applied to any pattern forming method or printing method, and the curable resin/curability is selected in order to obtain a resin composition having a viscosity and a surface tension suitable for each printing method. Additives such as monomers or solvents or surfactants. Further, the printing machine is selected in accordance with the printing accuracy, resolution, and the like of the light shielding film pattern.

For example, in the case of forming a light-shielding film by an inkjet printing method, the present invention Since the particles such as the light-shielding black particles or the color-adjusting particles contained in the composition are less agglomerated, the ink jet nozzles during intermittent ejection are less occluded, and the viscosity at the time of storage is stable over time, thereby contributing to continuous The stability of the pattern film thickness at the time of printing. Regarding the ink jet device, if the amount of the liquid discharged from the composition can be adjusted, there is no special In addition, in the ink jet head of a piezoelectric element which is generally used frequently, the physical properties of the ink composition which stably forms droplets vary depending on the configuration of the head, and the viscosity is 3 mPa at the temperature inside the head. Sec~150mPa. Sec can be, preferably 4mPa. Sec~30mPa. Sec. If the viscosity value becomes larger than this, the liquid droplets cannot be ejected; conversely, if the viscosity value becomes smaller than this, the discharge amount of the liquid droplets is not stable. Further, the temperature inside the head is also different depending on the stability of the ink composition to be used, and it is preferably used at 20 ° C to 45 ° C. In order to increase the thickness of the solid content in the ink composition, the film thickness is increased, and in order to maintain the viscosity of the discharge stably, a temperature of about 35 ° C to 40 ° C is generally used.

The characteristics of the composition as described above may be mainly by the solvent constituting the same or In order to suppress the drying of the composition of the nozzle portion during continuous printing, the solvent is mainly composed of a solvent having a boiling point of 180 ° C or higher, and the solvent having a boiling point of 180 ° C or higher can be 60 in all solvent components. % or more, preferably 80% or more, used alone or in combination. For the solvent having a boiling point of 180 ° C or higher, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate; ethylene glycol monomethyl ether, diethylene glycol monoethyl ether or the like Dialkyl glycol monoalkyl ether acetates such as alkyl ethers; diethylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters; other ethers such as diethylene glycol dimethyl ether; high-boiling solvents such as γ-butyrolactone.

The black tree of the present invention if it is used in the inkjet method An example of the composition ratio of the solid content of the lipid composition is 25% by mass to 60% by mass of the (A) curable resin and/or curable monomer, and black shading in the component (B). The optical particles may be in a range of from 15% by mass to 14% by mass, and the component for color adjustment in the component (C) may be in the range of from 1% by mass to 14% by mass, and more preferably the component (A) is in an amount of from 35% by mass to 55% by mass. The black light-shielding particles in the component (B) are 40% by mass to 60% by mass, and the color-adjusting particles in the component (C) are 1% by mass to 12% by mass. Further, 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 the component (A), (A-1)/ (A-2) may be in the range of 10/90 to 90/10, and preferably in the range of 30/70 to 70/30. Further, 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 physical properties such as surface hardness or mechanical properties of the cured product. In the case of 100 parts by mass of [(A-1)+(A-2)], it is preferred to use an epoxy resin in a range of from 1 part by mass to 60 parts by mass, more preferably from 10 parts by mass to 50 parts by mass. range.

On the other hand, in the photolithography method, the component (A) is a photocurable resin or The photocurable monomer is further mixed with an alkali-soluble resin which is dissolved in an alkaline developing solution. Further, an alkali-soluble resin containing an unsaturated group having an acidic group such as a polymerizable unsaturated group or a carboxyl group in the molecule is preferably used. For example, a wide range of resins including an alkali-soluble resin containing an unsaturated group which is polymerizable in one molecule such as glycidyl (meth)acrylate can be used. A resin obtained by reacting a compound having an unsaturated group and an epoxy group with a part of a carboxyl group of a resin obtained by radically copolymerizing (meth)acrylic acid with a (meth) acrylate compound.

Hardening method of light-shielding film formed on transparent substrate and hardening tree The fat component (A) is selected so as to suit the heat resistance of the transparent substrate, the environment to be used, the required dimensional accuracy, and reliability.

Regarding the hue and chromaticity of the black cured product (light-shielding film) thus obtained, in order to adjust black to achromatic or bluish-black, it is necessary to adjust the b ^* value in the CIE Lab color space representation system to -1.0. <b ^* < 0.2, more preferably -1.0 < b ^* <0.0. Further, as a method of measuring the b ^* value of the present invention, a D65 light source (a solar standard light source (light for color measurement) of JIS Z8720) or a C light source (JIS) for indicating the color of an object illuminated by sunlight is used. The daylight-assisted light source of Z8720 is a value measured from the opposite side of the surface on which the light-shielding film is applied to the light-shielding film obtained above, and is measured at a viewing angle of 2° or 10°.

Regarding the use of the black resin group for a light-shielding film of the present invention in photolithography In the case of the black photosensitive resin composition in the case of the product, the black photosensitive resin composition contains the components (A) to (E) as the main component. In the black photosensitive resin composition, (A-1) contains a polymerizable unsaturated group in a solid component other than the (D) solvent (including a polymerizable monomer component which becomes a solid component after photocuring). The alkali-soluble resin is 10% by mass to 60% by mass, and the (A-2) photopolymerizable monomer is 10 parts by mass to 60 parts by mass relative to (A-1) 100 parts by mass, relative to (A- 1) The (E) photopolymerization initiator is 2 parts by mass to 50 parts by mass, based on 100 parts by mass of the total amount of (A-2). More preferably, (A-2) is 15 parts by mass to 35 parts by mass, based on 100 parts by mass of (A-1), and is 100 parts by mass based on the total amount of (A-1) and (A-2). (E) is 5 parts by mass to 30 parts by mass. Moreover, regarding the black shading property in the component (B) The content of the particles is preferably in the range of 30% by mass to 60% by mass, and more preferably in the range of 40% by mass to 50% by mass based on the solid content other than the solvent (D). In addition, the color-adjusting particles in the component (C) are preferably in a range of 1% by mass to 15% by mass, and more preferably 2% by mass to 7% by mass, based on the solid content other than the (D) solvent.

Formation of a cured film using the black photosensitive resin composition of the present invention The method can be exemplified by a method using photolithography. The formation method is as follows: First, a black photosensitive resin composition is applied onto the surface of the substrate, and then the solvent is dried (prebaked), and then the obtained coating film is irradiated with ultraviolet rays through a photomask to harden the exposed portion. The development is performed by using an alkaline aqueous solution to elute the unexposed portion, thereby forming a pattern and further performing thermal curing (post-baking). Here, as the substrate to which the black photosensitive resin composition is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.) or the like is used.

A method of applying a black photosensitive resin composition onto a substrate In addition to the known solution dipping method and spraying method, any method such as a roll coater, a sand coater, a slit coater or a rotary machine may be employed. This can be carried out by applying these methods to a desired thickness, and then removing the solvent (prebaking) to form a coating film. After the prebaking, the solvent is removed by vacuum drying (VCD) at 20 Pa to 100 Pa for 15 seconds to 60 seconds, and then heated by an oven, a hot plate or the like. The heating temperature and the heating time in the prebaking can be appropriately selected depending on the solvent to be used, for example, at a temperature of 60 ° C to 110 ° C for 1 minute to 3 minutes.

The exposure after prebaking can be performed by an exposure machine, via a photomask Exposure is performed to thereby expose a portion of the photosensitive resin and the photosensitive monomer corresponding to the pattern. It is suitable to select an exposure machine and its exposure and irradiation conditions, and use an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp or the like to perform exposure.

Alkaline development after exposure is to remove the unexposed portion of the coating film For this purpose, the development is used to form a desired pattern. The developing solution suitable for the alkaline development includes, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and it is particularly preferable to use 0.03 mass% to 1 mass% of sodium carbonate or potassium carbonate. The weakly alkaline aqueous solution of the carbonate is developed at a temperature of 23 ° C to 27 ° C, and a fine image can be precisely formed using a commercially available developing machine or an ultrasonic cleaner.

After development as described above, at a temperature of 200 ° C to 240 ° C, 20 Heat treatment (post-baking) is carried out in a minute to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black film and the substrate. This can be carried out by heating using an oven, a hot plate or the like. Further, a target substrate with a light shielding film is thus obtained.

Regarding the hue and chromaticity of the black cured product (light-shielding film) thus obtained, in order to adjust black to achromatic or bluish-black, it is necessary to adjust the b ^* value in the CIE Lab color space representation system to -1.0. <b ^* < 0.2, more preferably -1.0 < b ^* <0.0. Further, as a method of measuring the b ^* value of the present invention, a D65 light source (a solar standard light source (light for color measurement) of JIS Z8720) or a C light source (JIS) for indicating the color of an object illuminated by sunlight is used. The solar-assisted light source of Z8720) was measured from the opposite surface side of the surface on which the light-shielding film was applied to the light-shielding film obtained above.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[Examples]

The various evaluations in the following examples were carried out as follows unless otherwise specified.

[solid content concentration]

1 g of the resin solution obtained in the synthesis example described later was impregnated into a glass filter [mass: W ₀ (g)], and weighed [W ₁ (g)], and the mass after heating at 160 ° C for 2 hr [W] ₂ (g)], which is obtained by the following formula.

Solid content concentration (% by mass) = 100 × (W _{2 -} W ₀ ) / (W _{1 -} W ₀ ).

[acid value]

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

[molecular weight]

Gel permeation chromatography (GPC) [manufactured by Tosoh Co., Ltd., trade name HLC-8220GPC], solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2) + TSKgel SuperH-3000 (1) + TSKgel SuperH-4000 (1) + TSKgel Super-H5000 (1) [Measured by Tosoh Co., Ltd., Temperature: 40 ° C, Velocity: 0.6 ml/min], the standard polystyrene (made by Tosoh Corporation, PS-oligomer kit) was used to determine the value. Weight average molecular weight (Mw).

[Average secondary particle size measurement]

The dispersion liquid containing the black light-shielding particles or the dispersion liquid containing the color-adjusting particles was measured and utilized by a particle size distribution meter (manufactured by Otsuka Electronics Co., Ltd., particle size analyzer FPAR-1000) by a dynamic light scattering method. The average secondary particle diameter obtained by the accumulation method. The dispersion liquid containing the light-shielding black particles or the dispersion liquid containing the color-adjusting particles is diluted to a sample for measurement so that the concentration of the particles dispersed in the propylene glycol monomethyl ether acetate is 0.1% by mass to 0.5% by mass. .

[Viscosity measurement]

The viscosity of the black resin composition for a light-shielding film was measured at 23 ° C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80L).

[Measurement of opacity (OD value)]

The glass substrate with a light-shielding film after post-baking was measured using the OD meter manufactured by Otsuka Electronics Co., Ltd.

[Measurement of film thickness]

The light-shielded glass substrate after post-baking was measured using a stylus type film thickness meter [manufactured by Tencor Co., Ltd.].

[Inkjet discharge stability test]

Insert the black mask with a black resin composition into Konica Minolta (Konica) In the piezoelectric element-driven inkjet head (14pL/drip; KM512M) manufactured by IJ, the rinsing and cleaning of the inkjet head ejection surface were carried out, and the ejection state of the ink composition was continuously observed by a flying observation camera for 30 minutes. Observe whether there are significant abnormalities such as not ejecting droplets, flying orbits are obviously not vertical. Further, the intermittent discharge test was carried out (the inkjet head ejection surface was washed and left to stand for 30 minutes, and the number of non-discharge nozzles when re-discharging was counted), and it was observed whether the number of non-discharge nozzles among all 512 nozzles was good. (within 10).

[Development Characteristics Evaluation]

The black resin composition of the light-shielding film was applied onto a glass substrate of 125 mm × 125 mm by a spin coater so that the film thickness after baking was 1.2 μm, and prebaking was performed at 80 ° C for 1 minute. Thereafter, the exposure gap was adjusted to 80 μm, a negative mask having a line/space of 20 μm/20 μm was coated on the dried coating film, and an ultraviolet ray of 100 mJ/cm ² was irradiated with an ultrahigh pressure mercury lamp having an I illuminance of 30 mW/cm ² . A photohardening reaction of the photosensitive portion is carried out. Next, the exposed coated plate was spray-developed at a pressure of 1 kgf/cm ² in a 0.05% potassium hydroxide aqueous solution at 23 ° C, and the time when the pattern was observed was taken as the development off time (BT seconds), and further 20 seconds was performed. After the development, the spray was washed with a pressure of 5 kgf/cm ² , the unexposed portion of the coating film was removed, and a pixel pattern was formed on the glass substrate, and then post-baking was performed at 230 ° C for 30 minutes using a hot air dryer. . The evaluation items and methods of the light-shielding films obtained in the respective examples and comparative examples are as follows.

Straightness of the pattern and smoothness of the surface of the coating: 20μ after post-baking was observed with a microscope and a scanning electron microscope (SEM) The line of m was judged to be "poor" when the sawtooth shape was observed, and the case where it was not jagged was judged as "good". Further, when there is unevenness in the thickness of the line film due to the coarse particles, the smoothness is judged as "poor".

Further, the omission symbols used in the synthesis examples and the like are as follows.

BPFE: a reaction of 9,9-bis(4-hydroxyphenyl)anthracene with chloromethyloxirane. In the compound of the formula (I), A is a compound of -9,9-diyl and R ₁ to R ₄ are hydrogen.

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP: triphenylphosphine

PGMEA: propylene glycol monomethyl ether acetate

BDGAC: diethylene glycol monobutyl ether acetate

DPHA: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [trade name DPHA manufactured by Nippon Kayaku Co., Ltd.]

HDDA: 1,6-hexanediol diacrylate

[Synthesis Example 1]

In a 500 ml four-necked flask equipped with a reflux condenser, 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 charged, and the mixture was heated at 100 ° C to 105 ° C for 12 hr. The reaction product was obtained by stirring.

Next, BPDA 25.01 g (0.085 mol) and THPA 12.93 g (0.085 mol) were placed in the obtained reaction product, and stirred under heating at 120 ° C to 125 ° C for 6 hr to obtain an alkali-soluble solution containing a polymerizable unsaturated group. Resin solution (A-1)-1. The solid content concentration of the obtained resin solution was 55.8 wt%, and the acid value (solid The body composition conversion was 103 mgKOH/g, and the Mw analyzed by GPC was 2,600.

[Preparation of Resin Solution: A-Component Solution]

The following resin solution A1 containing the component (A) and the resin solution A2 were prepared.

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

82.9 parts by mass of BDDAC, an alkali-soluble resin solution (A-1)-1 containing 6.3 parts by mass of a polymerizable unsaturated group, and a phenol novolac type epoxy resin [manufactured by Mitsubishi Chemical Corporation, trade name: JER154, epoxy The equivalent number is 178, and the average number of functional groups in one molecule is 3.0] 3.2 parts by mass, DPHA is 4.0 parts by mass, and 10% of the trade name BYK (registered trademark)-333 manufactured by BYK-Chemie Japan Co., Ltd. A resin solution A1 was prepared by mixing 1.24 parts by mass of BDGAC diluted solution and 2.95 parts by mass of 3-ureidopropyltriethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-585].

(2) Resin solution A2 (for photolithography: exposure/thermosetting resin composition)

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), and BYK Chemical Co., Ltd. 10% BDGAC diluted solution of the trade name BYK (registered trademark)-333 manufactured by the company, 1.24 parts by mass, 3-ureidopropyltriethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-585] 2.95 parts by mass was mixed to prepare a resin solution A2.

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

(1) Dispersion B1 containing black light-shielding particles (for inkjet printing): In the BIGAC, the carbon black concentration was 25 wt%, and the polymer dispersant was 10 wt%, and the dispersion was carried out in a bead mill to prepare a dispersion B1 containing black light-shielding particles. The average secondary particle diameter of the carbon black in the obtained dispersion was 96 nm.

(2) Dispersion B2 (for black lithography) containing black light-shielding particles: dispersed in a bead mill so that the carbon black concentration in PGMEA is 25% by weight and the polymer dispersant is 10% by weight. A dispersion B2 containing black light-shielding particles was formed. The average secondary particle diameter of the carbon black in the obtained dispersion was 111 nm.

[Preparation of dispersion containing particles for color adjustment: (C) component]

A dispersion liquid C1 containing color-adjusting particles and a dispersion liquid C4 containing color-adjusting particles were prepared by using a bead mill using a C.I. pigment yellow pigment PY139 and a polymer dispersant in PGMEA or BDGAC. The composition and characteristics of each dispersion are shown in Table 1.

[Preparation and Evaluation of Black Resin Composition for Light-Shielding Film and Its Light-Shielding Film] [Example 1 to Example 2]

12.8 parts by mass of the resin solution A1, 13.5 parts by mass of the carbon black dispersion B1, 3.8 parts by mass of the PY139 dispersion C1, and the cerium oxide dispersion S1 (NANOBYK-3605 manufactured by BYK) 0.5 parts by mass was mixed and subjected to pressure filtration using a 1 μm depth filter to prepare an ink for a light-shielding film (black resin composition for a light-shielding film). The initial viscosity (room temperature) of the ink produced was 10.3 mPa. Sec [23 ° C, measured with an E-type viscometer (Dongji Industry)]. The light-shielding film was applied onto the alkali-free glass by spin coating to change the number of revolutions, and these were dried at 90 ° C for 5 minutes, and further baked at 230 ° C for 30 minutes to form a glass substrate with a light-shielding film. . A film thickness of 1.1 μm was used as the sample of Example 1, and a film thickness of 1.4 μm was used as the sample of Example 2. The composition of each sample is shown in Table 2, and the evaluation results of each sample are shown in Table 3.

In addition, the measurement of the reflection optical characteristics in Table 3 was performed in the following manner.

[Measurement of Reflective Optical Properties]

After the post-baking glass substrate with a light-shielding film, a colorimeter CM2600d manufactured by Konica Minolta was used at a D65 light source, 10° field of view from the side of the opposite side of the surface on which the light-shielding film was formed. The measurement was carried out.

[Comparative Example 1]

In the same manner as in Example 1, except that the dispersion liquid containing PY139 was used, the light-shielding film ink (black resin composition for light-shielding film) was prepared by mixing the mass parts shown in Table 2. The light-shielding film was applied onto an alkali-free glass, dried at 90 ° C for 5 minutes, and further post-baked at 230 ° C for 30 minutes to prepare a glass substrate with a light-shielding film. The resulting film thickness was 1.3 μm. The sample evaluation results are shown in Table 3.

As shown in Table 3, in the first to second embodiments, the substrate with a light-shielding film also showed a light-shielding degree of 3 or more, and b ^{* was} also -0.08 and was close to zero. In contrast, in Comparative Example 1, b ^* More than 0.2.

[Example 3 to Example 4, Comparative Example 2 to Comparative Example 3]

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

When the average secondary particle diameter of PY139 is lower than the average secondary particle diameter of carbon black of 96 nm, it is -1.0 < b ^* < 0.2, whereas the average secondary particle diameter of PY139 exceeds the average of carbon black. In the case of each comparative example of the secondary particle diameter, the result of b ^* exceeding 0.2 was obtained.

[Examples 5 to 6]

The light-shielding ink was prepared in the same manner as in Example 1 except that the additive mass of PY139 in the dispersion liquid containing the particles for color adjustment was changed with respect to the mass of the carbon black particles. Further, in the same manner as in Example 1, a black resin composition for a light-shielding film was formed to form a light-shielding film on the alkali-free glass. The evaluation results are shown in Table 3. In any case, b ^{* was} shifted to the negative side as compared with Comparative Example 1 in which PY139 particles were not coexistent, and it was shown to be -1.0 <b ^* <0.2.

[Example 7 to Example 9, Comparative Example 4]

The light-shielding ink (black resin composition for light-shielding film) was prepared using the resin solution (A2) for photolithography printing using the composition shown in Table 2. The black resin composition of the light-shielding film was applied onto a glass substrate of 125 mm × 125 mm by a spin coater so that the film thickness after baking was 1.0 μm to 1.3 μm, and prebaking was performed at 80 ° C for 1 minute. Thereafter, the exposure gap was adjusted to 80 μm, a negative mask having a line/space of 20 μm/20 μm was coated on the dried coating film, and an ultraviolet ray of 100 mJ/cm ² was irradiated with an ultrahigh pressure mercury lamp having an I illuminance of 30 mW/cm ² . A photohardening reaction of the photosensitive portion is carried out. Next, the exposed coated plate was spray-developed at a pressure of 1 kgf/cm ² in a 0.05% potassium hydroxide aqueous solution at 23 ° C, and the time when the pattern was observed was taken as the development off time (BT seconds), and further 20 seconds was performed. After the development, the spray was washed with a pressure of 5 kgf/cm ² , the unexposed portion of the coating film was removed, and a pixel pattern was formed on the glass substrate, and then post-baking was performed at 230 ° C for 30 minutes using a hot air dryer. .

In the substrate with a light-shielding film containing PY139 particles, b ^* showed -1.0 <b ^* < 0.2, whereas in the substrate with a light-shielding film containing no PY139, b ^* exceeded 0.2.

[Evaluation of inkjet ejectability and development characteristics]

The light-shielding film prepared in Example 1 to Example 6 was placed in a piezoelectric element-driven ink-jet head (14 pL/drip; KM512M) manufactured by Konica Minolta IJ. After the rinsing and the cleaning of the inkjet head ejection surface were carried out, the ejection state of the ink composition was continuously observed with a flying observation camera for 30 minutes, and no significant abnormality such as no droplets were ejected and the flying orbit was not substantially vertical. Further, according to the intermittent discharge test (the inkjet head discharge surface is washed and left to stand for 30 minutes, and the number of non-discharge nozzles when re-discharging is counted), the number of non-discharge nozzles among all the 512 nozzles is two or less. It was found that no problem was found in ink jet ejectability at all.

Further, regarding the black resin composition for a light-shielding film prepared in Examples 7 to 9, the development characteristics (pattern linearity and smoothness of the surface of the coating film) were evaluated by the above method, and the results were confirmed to be linear and smooth. There is no problem with sex.

Further, the black photosensitive resin composition for a light-shielding film for photolithography is collectively shown for evaluation.

[Production of black photosensitive resin composition]

The black photosensitive resin compositions of Examples 8 to 10, Comparative Example 5, and Comparative Example 6 were prepared by blending the compositions shown in Table 4. The components used in each composition are shown below.

(A-1) Alkali-soluble resin solution: the alkali-soluble resin solution (A-1)-1 containing a polymerizable unsaturated group prepared in Synthesis Example 1.

(A-2) Photopolymerizable monomer: DPHA

(B) Black light-shielding particle dispersion liquid: carbon black dispersion of PGMEA solvent having a carbon black content of 25% by mass and a polymer dispersant of 6% by mass

(C) Particle dispersion liquid for color adjustment:

(C)-1: Yellow pigment dispersion of PGMEA solvent having Y139 (average secondary particle diameter of 108 nm) of 15% by mass and polymer dispersant of 9% by mass

(C)-2: Yellow pigment dispersion of PGMEA solvent in which Y139 (average secondary particle diameter: 123 nm) is 15% by mass and polymer dispersant is 9% by mass

(C)-3: Yellow pigment dispersion of PGMEA solvent in which Y139 (average secondary particle diameter: 158 nm) is 15% by mass and polymer dispersant is 9% by mass

(C)-4: Solvent Blue 45 (blue dye: powder)

(D) Solvent: a mixed solvent of PGMEA and cyclohexanone

(E) Photopolymerization initiator: 1-[9-ethyl-6-(2-methylbenzhydryl)oxazol-3-yl]ethanone=O-acetamidine (manufactured by BASF Corporation, trade name Irgacure OXE02)

(F) Surfactant: 1% PGMEA solution

(G) decane coupling agent

[Evaluation of reflection color]

The black photosensitive resin compositions of Examples 8 to 10, Comparative Example 5, and Comparative Example 6 were spin-coated on a glass plate (5-inch square), and dried at 90 ° C for 1 minute with a hot plate. Post-baking was carried out at 230 ° C for 30 minutes. A black cured product having a thickness of 1.45 μm was obtained as described above.

The reflection color measurement was carried out using UH-4100 manufactured by Hitachi High-Technologies Co., Ltd. using the entire substrate of the black cured product. The light source is a C light source (2° field of view) or a D65 light source (10° field of view).

In Comparative Example 5, the chromaticity of the reflection color of only the black light-shielding particles was shown. However, in order to make it achromatic, there is a need to make a ^* and b ^* close to 0, especially when the reflection color deviates from achromatic color. In some cases, a blue hue is more required than the brown color, and according to this, it is understood that there is a need to make b ^* a value of -. On the other hand, in the eighth to tenth embodiments, it is possible to prevent the a ^{* of} the reflected color from being largely changed by adding the yellow color adjusting particles having the chromaticity of the same color as the black light-shielding particles. The ground moves b ^* to the side (negative side). Further, it is understood that in order to make b ^* from a black color to a blue hue, it is preferable to control the range of -1.0 <b ^* <0.2, and it can be realized by the present invention in the eighth to tenth embodiments. Further, in order to make it a blue hue, it is more preferable to adjust it to 1.0 <b ^* <0.0, and it can control by controlling the average secondary particle diameter of the black light-shielding particle and the color adjustment particle.

On the other hand, when the blue dye having the opposite color chromaticity of the black light-shielding particles (dissolved in a solvent and not being a particle in the composition) is added as in Comparative Example 6, the value of b ^* is inversely increased. The reflected color is moved in the opposite direction to the achromatic direction, and the desired achromatic or a plurality of blue hue cannot be obtained.

Therefore, as shown in the present invention, it is understood that the color of the black cured product can be adjusted to be achromatic or a desired hue by merely selecting the color adjusting particles which are the same color as the black light-shielding particles and adding them in a small amount.

Claims (9)

A black resin composition for a light-shielding film, comprising the following components as an essential component: (A) a curable resin using light or heat, and/or a curable monomer using light or heat, and (B) a dispersion medium. A dispersion liquid containing black light-shielding particles obtained by dispersing black light-shielding particles and (C) a dispersion liquid containing color adjustment particles obtained by dispersing particles for color adjustment in a dispersion medium. The black resin composition for a light-shielding film according to the first aspect of the invention, wherein the average secondary particle diameter D _C of the color-adjusting particles in the component (C) and the average of the black light-blocking particles in the component (B) The ratio D _C /D _B of the secondary particle diameter D _{B is} in the range of 0.2 to 1.2, and the mass m _C of the color-adjusting particles contained in the component (C) and the black light-shielding particles contained in the component (B) The ratio m _C /m _B of the mass m _{B is} in the range of 0.03 to 0.2. The black resin composition for a light-shielding film according to the first or second aspect of the invention, wherein the black light-shielding particles are carbon black. The black resin composition for a light-shielding film according to the first or second aspect of the invention, wherein the color-adjusting particles are C.I. Pigment Yellow 139 as a yellow pigment and/or C.I. Pigment Orange 61 as an orange pigment. A black resin composition for a light-shielding film, characterized in that the black resin composition for a light-shielding film is an alkali-soluble resin containing a polymerizable unsaturated group and a polymerizable monomer having an ethylenically unsaturated double bond (A). And a black resin composition for a light-shielding film according to any one of claims 1 to 4, which further comprises (D) a solvent and (E) a photopolymerization initiator, and contains photohardening In the solid content of the polymerizable monomer which is a solid polymer, the alkali-soluble resin containing a polymerizable unsaturated group is 10% by mass to 60% by mass, and contains a polymerizable unsaturated group. 100 parts by mass of the alkali-soluble resin, the polymerizable monomer having an ethylenically unsaturated double bond is 10 parts by mass to 60 parts by mass, relative to the alkali-soluble resin containing a polymerizable unsaturated group and having an ethylenically unsaturated double (E) is 2 parts by mass to 50 parts by mass, and further, among the solid components, the black light-blocking particles in the component (B) are 30% by mass to 60% by mass based on 100 parts by mass of the total amount of the polymerizable monomers of the bond. % is 1% by mass to 15% by mass of the particles for color adjustment in the component (C) in the solid content. The black resin composition for a light-shielding film according to claim 5, wherein the alkali-soluble resin containing a polymerizable unsaturated group is used as (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) four A polymerizable unsaturated group obtained by reacting a carboxylic acid or an acid dianhydride thereof with a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid containing an unsaturated group Alkali soluble resin. A substrate with a light-shielding film, wherein the substrate with a light-shielding film is coated on a transparent substrate with a black resin composition for a light-shielding film according to any one of claims 1 to 6. a substrate with a light-shielding film obtained by hardening one surface thereof, and a substrate with a light-shielding film in a CIE Lab color space system measured from the opposite side of the surface of the transparent substrate on which the light-shielding film is applied The b ^* value satisfies -1.0 <b ^* <+0.2. A color filter comprising the substrate with a light shielding film according to claim 7 of the patent application. A touch panel comprising the substrate with a light shielding film according to claim 7 of the patent application.