Photosensitive resin composition for black resist

Abstract

To provide a photosensitive resin composition for a black resist which has high light-shielding property and low reflectance, and can suppress occurrence of an aggregate.SOLUTION: A photosensitive resin composition for a black resist contains (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one kind of light-shielding component selected from a black pigment, a mixed color pigment and a light-shielding material, (E) silica particles, and (F) a solvent. The (F) solvent contains a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent having a relative dielectric constant at 23°C of 10 to 30, and the relative dielectric constant at 23°C of (F) the whole solvent is 8.5 or more.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, with the development of mobile terminals, the number of display devices such as touch panels and liquid crystal panels used outdoors and in vehicles has been increasing. In the above display device, a light-shielding film is provided on the outer frame of the touch panel to shield light leakage from the peripheral portion of the liquid crystal panel on the back surface. In the liquid crystal panel, a black matrix is provided to suppress light leakage from the screen during black display and to suppress color mixing between adjacent color resists.

[0003] In a display device or the like, in order to suppress light leakage and improve the visibility of the screen of the display device or the like, the concentration of the black pigment in the light-shielding film may be increased to improve the light-shielding property of the light-shielding film (reduce the light transmittance of the light-shielding film). Since the refractive index of the black pigment is higher than that of the transparent base material or the curable resin, when the concentration of the black pigment in the light-shielding film is increased, the reflectance when viewed from the side opposite to the surface on which the light-shielding film of the transparent base material is formed becomes high. Therefore, reflection at the interface between the light-shielding film formed on the transparent base material and the transparent base material increases, and problems such as reflection on the light-shielding film and the black matrix boundary being conspicuous due to the difference in reflectance from the colored portion of the color filter occur.

[0004] Therefore, there is a demand for a photosensitive resin composition for black resist having both high light-shielding property and low reflectance, a light-shielding film formed by curing the same, and a color filter.

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition characterized by containing hydrophobic silica particles and a specific dispersant (urethane-based dispersant). According to Patent Document 1, by using hydrophobic silica particles and a specific dispersant, a black matrix that achieves both high light-shielding properties and low reflectivity can be formed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, as a result of the inventors' study, it was not possible to obtain a light-shielding film having both the desired light-shielding properties and reflectivity with the black photosensitive resin composition described in Patent Document 1. Further, in the black photosensitive resin composition described in Patent Document 1, aggregates derived from silica particles were generated, which could cause light leakage in thick lines and frame parts and foreign matters in openings.

[0008] Therefore, as a result of intensive studies to solve the problems in conventional photosensitive resin compositions, the inventors found that silica particles have the characteristic of easily aggregating through silanol groups present on the particle surface, and generally, it is possible to disperse them in an organic solvent by coating with a silane coupling agent. However, it is difficult to coat all the silanol groups present on the surface with a silane coupling agent, and when mixed with a resin composition having different polarities, the dispersion state becomes unstable and tends to aggregate. By mixing a polar solvent having a high relative dielectric constant as a resist solvent within an appropriate range, it was found that the silanol groups on the surface of the silica particles can be stabilized by solvation, and aggregation of the silica particles can be suppressed.

[0009] The present invention has been made in view of such a point, and provides a photosensitive resin composition for black resist having high light-shielding properties and low reflectance, capable of suppressing the generation of aggregates, a light-shielding film obtained by curing the composition, a color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel.

Means for Solving the Problems

[0010] The photosensitive resin composition for black resist according to the present invention contains, as essential components, (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, mixed-color pigments, and light-shielding materials, (E) silica particles, and (F) a solvent. The (F) solvent includes a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent having a relative dielectric constant at 23°C of 10 to 30, and the relative dielectric constant at 23°C of the entire (F) solvent is 8.5 or more.

[0011] The light-shielding film according to the present invention is obtained by curing the above photosensitive resin composition for black resist.

[0012] The color filter according to the present invention has the above light-shielding film as a black matrix.

[0013] The touch panel according to the present invention has the above light-shielding film as a black matrix.

[0014] The display device according to the present invention has the above color filter or the above touch panel.

Effects of the Invention

[0015] According to the present invention, it is possible to provide a photosensitive resin composition for black resist having high light-shielding properties and low reflectance and capable of suppressing the generation of aggregates, a light-shielding film obtained by curing the composition, a color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel.

Embodiments for Carrying Out the Invention

[0016] Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resist of the present invention (hereinafter abbreviated as the photosensitive resin composition) contains, as essential components, (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, mixed pigments, and light-shielding materials, (E) silica particles, and (F) a solvent. Hereinafter, the components (A) to (F) will be described.

[0017] 1. Component (A) The unsaturated group-containing photosensitive resin, which is the component (A) according to the present embodiment, preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxy group. If it is the above resin, it can be widely used without particular limitation.

[0018] Examples of the above unsaturated group-containing photosensitive resin include an epoxy (meth) acrylate acid adduct obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter also referred to as "bisphenol type epoxy compound represented by the general formula (1)") with (meth) acrylic acid and then reacting the resulting compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. Note that "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and means one or both of them.

[0019] The unsaturated group-containing photosensitive resin as the component (A) is preferably an unsaturated group-containing photosensitive resin obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the general formula (1) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride.

[0020]

Chemical formula

[0021]

Chemical formula

[0022] The bisphenol type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. In this reaction, since oligomerization of the diglycidyl ether compound generally occurs, it contains an epoxy compound containing two or more bisphenol skeletons.

[0023] Examples of bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)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, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like.Among these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0024] Examples of (a) dicarboxylic acid or acid anhydride of tricarboxylic acid that reacts with the hydroxy group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include acid anhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid anhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, acid anhydrides of aromatic dicarboxylic acids or tricarboxylic acids, and the like. Here, examples of acid anhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides 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, and diglycolic acid. Furthermore, it includes acid anhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced. Examples of acid anhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid anhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. Furthermore, it also includes acid anhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced. Examples of acid anhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid, isophthalic acid, and trimellitic acid. Furthermore, it includes acid anhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0025] In addition, as the acid dianhydride of (b) tetracarboxylic acid to be reacted with epoxy (meth) acrylate, an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, or an acid dianhydride of an aromatic tetracarboxylic acid is used. Here, examples of the acid dianhydride of a chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced. Examples of the acid dianhydride of an alicyclic tetracarboxylic acid include acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced. Examples of the acid dianhydride of an aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenyl ether tetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced.

[0026] The molar ratio (a) / (b) of the acid anhydride of (a) dicarboxylic acid or tricarboxylic acid to be reacted with epoxy (meth) acrylate and the acid dianhydride of (b) tetracarboxylic acid is preferably 0.01 or more and 10.0 or less, and more preferably 0.02 or more and less than 3.0. When the molar ratio (a) / (b) is within the above range, an optimum molecular weight for obtaining a photosensitive resin composition having good patterning properties can be obtained. Note that the smaller the molar ratio (a) / (b), the larger the molecular weight and the more likely the alkali solubility is to decrease.

[0027] In addition, the reaction between the epoxy compound and (meth)acrylic acid, and the reaction between the epoxy (meth)acrylate obtained from this reaction and the polybasic carboxylic acid or its acid anhydride are not particularly limited, and known methods can be adopted. Further, for the unsaturated group-containing photosensitive resin synthesized by the above reaction, its weight average molecular weight (Mw) is preferably 2000 to 10000, and its acid value is preferably 30 to 200 mgKOH / g. The weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin can be determined, for example, using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). Also, the acid value of the unsaturated group-containing photosensitive resin can be determined, for example, using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0028] Another example of a preferred resin as the unsaturated group-containing photosensitive resin of component (A) includes copolymers such as (meth)acrylic acid and (meth)acrylic acid esters, and resins having (meth)acryloyl groups and carboxyl groups. Examples of the above resins include copolymers obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting (meth)acrylic acid, and finally reacting with an anhydride of a dicarboxylic acid or tricarboxylic acid, including polymerizable unsaturated group-containing alkali-soluble resins. The above copolymer is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g, as shown in JP-A-2014-111722, and a polymerizable unsaturated group-containing alkali-soluble resin which is a polymer having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mgKOH / g, including units derived from (meth)acrylic acid ester compounds and units having (meth)acryloyl groups and di- or tricarboxylic acid residues, as shown in JP-A-2018-141968, can be referred to.

[0029] Regarding the unsaturated group-containing photosensitive resin of component (A), only one type may be used alone, or two or more types may be used in combination.

[0030] 2. Component (B) Examples of the photopolymerizable monomer having at least two or more unsaturated bonds in component (B) according to this embodiment include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylic acid esters, and dendritic polymers having a (meth)acrylic group as a compound having an ethylenic double bond. Only one type of these photopolymerizable monomers may be used alone, or two or more types may be used in combination. Further, the photopolymerizable monomer having at least two ethylenic unsaturated bonds can play a role of crosslinking the molecules of the polymerizable unsaturated group-containing alkali-soluble resin, and in order to exhibit this function, it is preferable to use those having three or more unsaturated bonds. Also, it is preferable that the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acryloyl groups in one molecule is 50 to 300 g / eq, and more preferably 80 to 200 g / eq. Note that component (B) does not have a free carboxy group.

[0031] (B) As compounds having unsaturated bonds that can be included in the composition, examples of dendritic polymers having a (meth)acryloyl group include dendritic polymers obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, it includes dendritic polymers obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the general formula (3) with a polyvalent mercapto compound represented by the general formula (4).

[0032]

Chemical formula

[0033]

Chemical formula

[0034] Examples of the polyfunctional (meth)acrylate represented by the general formula (3) include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate. These compounds may be used alone, or two or more of them may be used in combination.

[0035] Examples of the polyvalent mercapto compound represented by the general formula (4) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercapto propionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercapto propionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercapto propionate), and the like. These compounds may be used alone, or two or more of them may be used in combination.

[0036] The blending ratio of component (A) and component (B) is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20 in terms of weight ratio (A) / (B). When the blending ratio of component (A) is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and in the unexposed part, the acid value of the coating film is less likely to decrease, so the decrease in solubility in the alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges or lack of sharpness are less likely to occur. Also, when the blending ratio of component (A) is 90 / 10 or less, the ratio of the photoreactive functional groups in the resin is sufficient, so the desired crosslinked structure can be formed. Also, since the acid value in the resin component is not too high, the solubility in the alkaline developer in the exposed part is less likely to increase, so the formed pattern can be prevented from becoming thinner than the target line width and the pattern can be prevented from being missing.

[0037] 3. Component (C) Examples of the (C) photoinitiator according to this embodiment include 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; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; imidazole - based compounds such as 2 - (o - chlorophenyl) - 4,5 - diphenylimidazole, 2 - (o - chlorophenyl) - 4,5 - di(m - methoxyphenyl)imidazole, 2 - (o - fluorophenyl) - 4,5 - diphenylimidazole, 2 - (o - methoxyphenyl) - 4,5 - diphenylimidazole, 2,4,5 - triarylimidazole; halomethylthiazole compounds such as 2 - trichloromethyl - 5 - styryl - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - cyanostyryl) - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - methoxystyryl) - 1,3,4 - oxadiazole; halomethyl - S - triazine - based compounds such as 2,4,6 - tris(trichloromethyl) - 1,3,5 - triazine, 2 - methyl - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - phenyl - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - chlorophenyl) - 4,6 - bis(trichloromethyl - 1,3,5 - triazine, 2 - (4 - methoxyphenyl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methoxynaphthyl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methoxystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (3,4,5 - trimethoxystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methylthioystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine;Etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime and other O-acyl oxime compounds; 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 azobisisobutyronitrile, benzoyl peroxide, cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine are included. These photoinitiators may be used alone or in combination of two or more of them.;

[0038] Examples of O-acyl oxime compounds that can be preferably used include O-acyl oxime photoinitiators represented by general formula (5) and general formula (6). Among these compounds, when a light-shielding component is used at a high concentration, it is preferable to use an O-acyl oxime photoinitiator having a molar extinction coefficient of 10,000 or more at 365 nm. In the present invention, the "photoinitiator" is used in a meaning including a sensitizer.

[0039] [Chemical formula] (In formula (5), R9, R10 each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 11 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be a linear, branched, or cyclic alkyl group.)

[0040]

Chemical formula

[0041] The amount of the photopolymerization initiator as component (C) is preferably 3 parts by weight or more and 30 parts by weight or less, more preferably 5 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight in total of the components (A) and (B). When the blending ratio of component (C) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be achieved. When the blending ratio of component (C) is 30 parts by weight or less, an appropriate sensitivity can be achieved, so that a desired pattern line width and a desired pattern edge can be obtained.

[0042] 4. Component (D) As the light-shielding components such as black pigments, mixed-color pigments, and light-shielding materials which are component (D) according to this embodiment, as long as they are dispersed with an average particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter), known light-shielding components can be used without particular limitation.

[0043] Examples of the black pigment as component (D) include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, and the like.

[0044] Examples of the mixed-color pigment as component (D) include pigments in which at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed.

[0045] The above-mentioned component (D) may be used alone as only one type thereof, or two or more types may be used in combination, depending on the function of the target photosensitive resin composition.

[0046] In addition, examples of the organic pigments that can be used when using a mixed-color pigment as component (D) include those with the following numbers by Color Index name, but are not limited thereto. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0047] (D) The blending ratio of the light-shielding component can be arbitrarily determined according to the desired light-shielding degree, but it is preferably 20% by weight or more and 80% by weight or less, and more preferably 40% by weight or more and 70% by weight or less, based on the solid content in the photosensitive resin composition. When using an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black as the light-shielding component of (D), it is particularly preferably 40% by weight or more and 60% by weight or less based on the solid content in the photosensitive resin composition. When the light-shielding component is 20% by weight or more based on the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light-shielding component is 80% by weight or less based on the solid content in the photosensitive resin composition, the content of the photosensitive resin that originally serves as the binder does not decrease, so the desired developing properties and film-forming ability can be obtained.

[0048] The above-mentioned component (D) is usually mixed with other compounding components as a light-shielding component dispersion dispersed in a solvent, and a dispersant can be added at that time. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation.

[0049] Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). In particular, the dispersant preferably has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary, or tertiary amino group as an adsorption point to the colorant, and is a cationic polymer dispersant having an amine value in the range of 1 to 100 mgKOH / g and a number average molecular weight (Mn) in the range of 1000 to 100000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the light-shielding component. Note that high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but those without dispersion promoting ability are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion. The amine value of the dispersant means the number of mg of KOH equivalent to the amount of acid (such as acetic acid) required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with JIS-K7237. Also, the number average molecular weight (Mn) of the dispersant can be determined, for example, using the above-mentioned gel permeation chromatography (GPC) "HLC-8220GPC".

[0050] 5. Component (E) The silica particles as component (E) are not particularly limited in terms of production methods such as gas-phase reaction or liquid-phase reaction, or shape (spherical, non-spherical).

[0051] The type of silica particles as component (E) used in the present invention is not particularly limited. Solid silica may be used, or hollow silica particles may be used. Note that "hollow silica particles" refer to silica particles having a cavity inside the particles.

[0052] By using the above silica particles, the refractive index of the light-shielding film containing the silica particles can be lowered.

[0053] The average particle diameter of the above silica particles is preferably 1 to 100 nm, more preferably 10 to 90 nm. Compared with the case of small particle diameters such as several nm, it is considered that aggregation of silica particles is less likely to occur at sizes within the above range. Thereby, in the range of the above particle diameter, since the silica particles are excellent in dispersion stability, they can be uniformly present in the light-shielding film. Therefore, variations in reflectance on the light-shielding film are less likely to occur.

[0054] The average particle diameter of the above silica particles can be measured by the cumulant method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) of the dynamic light scattering method.

[0055] Also, the content of the above silica particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, good patterning properties can be ensured while achieving a lower reflectance.

[0056] Also, silica particles having a refractive index of 1.10 to 1.47 can be used. In addition to using silica particles having a refractive index of 1.45 to 1.47, which is the refractive index of ordinary silica particles, by using hollow silica particles having a low refractive index, the refractive index of the light-shielding film can be made lower than that of a light-shielding film containing only ordinary silica particles.

[0057] Also, the refractive index of the silica particles can be obtained from a transparent mixture obtained by mixing the above silica particles processed into a powder form with a standard refractive liquid having a known refractive index. In this case, the refractive index of the standard refractive liquid of the above mixture is taken as the refractive index of the silica particles. The refractive index of the above silica particles can be measured using an Abbe refractometer.

[0058] In addition, since the photosensitive resin composition contains silica particles, reflection caused by the difference in refractive index between the transparent substrate and the light-shielding film formed thereon can be suppressed. Therefore, reflection can be suppressed without separately providing an antireflection film or the like on the substrate.

[0059] The shape of the silica particles may be a spherical shape or an elliptical shape. The shape of the silica particles used in the present invention is preferably a spherical shape.

[0060] The sphericity of the silica particles is preferably 1.0 to 1.5. If the sphericity of the silica particles is within this range, the particle shape becomes close to a sphere. Therefore, it can be uniformly filled in a light-shielding film with a thin film thickness, and a light-shielding film can be formed in which the silica particles are not exposed to the outside from the film surface while maintaining the surface smoothness of the film. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained.

[0061] The sphericity of the silica particles can be determined from the ratio of the longest diameter to the shortest diameter of the particles (average value of any 100 silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values obtained by photographing the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the silica particles from the obtained micrograph.

[0062] 6. Component (F) The solvent as component (F) contains a first solvent which is propylene glycol monomethyl ether acetate and a second solvent having a relative permittivity of 10 to 30 at 23°C.

[0063] (F) Among the solvents, the first solvent is propylene glycol monomethyl ether acetate. The content of the first solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 20 to 74% by mass with respect to the total mass of the (F) component. By containing 10 to 90% by mass of propylene glycol monomethyl ether acetate as the first solvent, the solubility of the binder resin and the dispersibility of the black pigment can be improved.

[0064] In addition, the relative permittivity of the second solvent at 23°C is 10 to 30, more preferably 13 to 20, and even more preferably 13 to 18. By using a solvent having a relative permittivity of 10 to 30 at 23°C as the second solvent, the silanol groups on the surface of the silica particles can be stabilized by solvation, and the aggregation of the silica particles in the resist composition can be suppressed.

[0065] The second solvent preferably contains saturated ketones having a linear, branched or cyclic structure with 3 to 12 carbon atoms, or saturated or unsaturated alcohols having a linear, branched or cyclic structure with 3 to 12 carbon atoms.

[0066] Examples of the second solvent include saturated ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; saturated alcohols such as ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, ethyl lactate, and 3-methoxy-3-methylbutanol; glycol ethers such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. Among the above second solvents, cyclohexanone, ethyl lactate, 3-methoxy-3-methylbutanol, and propylene glycol monoethyl ether are preferred, and cyclohexanone, ethyl lactate, and 3-methoxy-3-methylbutanol are more preferred.

[0067] The content of the second solvent is preferably 10 to 50% by mass, more preferably 20 to 50% by mass, and even more preferably 25 to 50% by mass based on the total mass of the (F) solvent. By setting the content of the second solvent within the above range, aggregation of silica particles can be suppressed while imparting good coatability.

[0068] The relative permittivity of the (F) solvent can be measured using a relative permittivity meter "Model871" (manufactured by Nippon Luft Co., Ltd.).

[0069] In addition, in this embodiment, the (F) solvent may include a third solvent having a boiling point at normal pressure of 150°C to 350°C other than the first solvent and the second solvent. The boiling point of the third solvent at normal pressure is preferably 150 to 350°C, and more preferably 160 to 300°C. By including the third solvent having a boiling point at normal pressure of 150 to 350°C, the drying property of the resist can be controlled, and bumping during vacuum drying and generation of drying foreign matters at the coater nozzle can be suppressed.

[0070] Examples of the third solvent include acetate esters such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monoethyl ether acetate, and ethyl 3-ethoxypropionate; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; and terpenes such as α- or β-terpineol. Among the above third solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether are preferred.

[0071] The content of the above third solvent is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the (F) solvent. By containing the third solvent in the range of 1 to 30% by mass, aggregation of silica particles can be suppressed.

[0072] Further, the relative permittivity of the entire (F) solvent at 23°C is preferably 8.5 or more and 15.0 or less, more preferably 8.8 or more and 15.0 or less, and even more preferably 9.3 or more and 15.0 or less. By setting the relative permittivity of the entire (F) solvent at 23°C to 8.5 or more, the silanol groups remaining on the surface of the silica particles can be stabilized by solvation, and aggregation of the silica particles can be suppressed. Also, by setting the relative permittivity at 23°C to 15.0 or less, the drying property and good coatability in the VCD process of drying the solvent under reduced pressure can be ensured. Here, "the entire solvent" means the mixed solvent of the first solvent and the second solvent, or the mixed solvent of the first solvent, the second solvent, and the third solvent.

[0073] In addition, the photosensitive resin composition of the present invention may contain, if necessary, resins other than the component (A) such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than silica, leveling agents, defoaming agents, surfactants, coupling agents and other additives can be blended.

[0074] Examples of resins other than component (A), such as epoxy resins, include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate. Polymers, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butane tetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a silicone skeleton, and the like. Examples of the curing agent include amine compounds, polyvalent carboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. that contribute to the curing of epoxy resins. Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, etc.Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, mica, alumina, and the like. Examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0075] The photosensitive resin composition of the present invention preferably contains, in the solid content excluding the solvent (the solid content includes monomers that become solid components after photocuring), an unsaturated group-containing photosensitive resin as component (A), a photopolymerizable monomer having at least two or more unsaturated bonds as component (B), a photoinitiator as component (C), at least one light-shielding component selected from a black pigment, a mixed-color pigment, and a light-shielding material as component (D), and (E) silica particles. The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass based on the total mass of the photosensitive resin composition.

[0076] In addition, the light-shielding film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent, and irradiating with light (including ultraviolet rays, radiation, etc.) to cure it. By using a photomask or the like to provide a portion irradiated with light and a portion not irradiated with light, only the portion irradiated with light is cured, and the other portion is dissolved in an alkaline solution, a desired pattern can be obtained.

[0077] In addition, a color filter or a touch panel having the light-shielding film of the present invention as a black matrix is produced, for example, by forming a light-shielding film with a film thickness of 1.0 to 2.0 μm on a transparent substrate, and forming each red, blue, and green pixel by photolithography after forming the light-shielding film, or by injecting red, blue, and green inks into the light-shielding film by an inkjet process.

[0078] The light-shielding film obtained by curing the photosensitive resin composition of the present invention can also be used as a black column spacer of a liquid crystal display device. For example, using a single black resist, a plurality of portions with different film thicknesses can be produced, and one can function as a spacer while the other functions as a black matrix.

[0079] Examples of the method for forming the light-shielding film obtained by curing the photosensitive resin composition of the present invention include the photolithography method. The photolithography method involves applying the photosensitive resin composition on a substrate, removing the solvent (pre-baking), applying a photomask on the resulting coating film, irradiating with radiation to cure the exposed portion, and further performing development to elute the unexposed portion using an aqueous alkali solution to form a pattern, followed by heat treatment (post-baking).

[0080] Examples of the above substrate include a glass substrate, a transparent film (for example, a transparent electrode such as ITO or gold is vapor-deposited or patterned on a polycarbonate, polyethylene terephthalate, polyethersulfone, etc.).

[0081] Examples of methods for applying a photosensitive resin composition to a substrate include known solution immersion methods, spray methods, methods using a roller coater, a land coater, a slit coater, a spinner, etc. By these methods, after coating to a desired thickness, a film is formed by removing the solvent (pre-baking). Pre-baking can be carried out by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in pre-baking can be appropriately selected according to the solvent used, but for example, it is preferably carried out at 80 to 120 °C for 1 to 10 minutes.

[0082] Exposure performed after pre-baking is carried out by an exposure apparatus. In photolithography, for example, exposure is carried out by exposing the coating film on the substrate through a photomask so that only the coating film in the portion corresponding to the pattern is sensitized, and the photosensitive resin composition contained in the coating film is photocured. As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc. can be used, but the wavelength range of the radiation is preferably 250 to 450 nm.

[0083] After exposure, the unexposed portion on the coating film is removed with a developer suitable for alkali development. As a developer suitable for alkali development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. These developers can be appropriately selected according to the characteristics of the resin layer, and it is also effective to add a surfactant as necessary. The development temperature is preferably 20 to 35 °C, and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, etc. After alkali development, it is usually washed with water. As the development treatment method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid bath) development method, etc. can be applied.

[0084] After development in this manner, heat treatment (post-baking) is performed at 180 to 250 °C for 20 to 100 minutes. This post-baking is carried out for purposes such as enhancing the adhesion between the patterned cured film (light-shielding film) and the substrate. This is done by heating with an oven, hot plate, etc., similar to pre-baking. The patterned cured film (light-shielding film) of the present invention is formed through each process by the photolithography method. Then, polymerization or curing (sometimes referred to as curing together) is completed by heat, and a light-shielding film having a desired pattern can be obtained.

[0085] As described above, the photosensitive resin composition for black resist of the present invention is not only suitable for forming a fine pattern by operations such as exposure and alkali development, but also a light-shielding film having similar excellent light-shielding properties, adhesion, electrical insulation, heat resistance, and chemical resistance can be obtained even when a pattern is formed by conventional screen printing.

[0086] The photosensitive resin composition for black resist of the present invention can be suitably used as a coating material. In particular, the ink for color filters used in liquid crystal display devices or imaging elements, and the light-shielding film formed thereby are useful as color filters, black matrices for liquid crystal projection, etc. Further, the photosensitive resin composition for black resist of the present invention can be used as an ink material for color separation or light shielding in various multicolor displays such as organic electroluminescence devices represented by organic EL elements, color liquid crystal display devices, color facsimiles, and image sensors, in addition to the color filter ink of color liquid crystal displays. According to the color filter of the present invention, reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, and reflection of light emitted from the element when used in an organic EL element, for example, can be reduced. That is, it is possible to realize an improvement in bright contrast by reducing the reflection of external light and an improvement in light emission efficiency by improving the light extraction efficiency from the light emission side.

Examples

[0087] Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

[0088] First, the synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin as the component (A) will be described. The evaluation of the resins in these synthesis examples was carried out as follows unless otherwise specified.

[0089] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)], and the weight [W2 (g)] after heating at 160 ° C for 2 hours was determined from the following formula. Solid content concentration (wt%) = 100×(W2 - W0) / (W1 - W0)

[0090] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10 N - KOH aqueous solution using a potentiometric titrator "COM - 1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to obtain the acid value.

[0091] [Molecular weight] Gel permeation chromatography (GPC) "HLC - 8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgel Super H - 2000 (2 pieces) + TSKgel Super H - 3000 (1 piece) + TSKgel Super H - 4000 (1 piece) + TSKgel Super H - 5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 ° C, flow rate: 0.6 ml / min) was used to measure the weight average molecular weight (Mw) as a value in terms of standard polystyrene (manufactured by Tosoh Corporation, PS - oligomer kit).

[0092] [Average particle size] The average particle size of the silica particles was determined by the cumulant method using a particle size distribution meter "Particle Size Analyzer FPAR - 1000" (manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.

[0093] The abbreviations used in the synthesis examples are as follows. BPFE: Reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In the compound of general formula (1), a compound where X is a fluorene-9,9-diyl group and R1 to R4 are hydrogen AA: Acrylic acid BPDA: 3,3’,4,4’-Biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0094] [Synthesis Example] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were charged into a 500 ml four-necked flask equipped with a reflux condenser, and stirred and reacted at 100 to 105 °C for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and stirred at 120 to 125 °C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A). The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mgKOH / g, and Mw by GPC analysis was 3600.

[0095] Photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were prepared with the compounding amounts (unit: mass%) shown in Tables 1 and 2. The compounding components used in the tables are as follows.

[0096] (Polymerizable unsaturated group-containing alkali-soluble resin) (A): Alkali-soluble resin solution obtained in the above synthesis example (solid content concentration 56.1% by mass)

[0097] (Photopolymerizable monomer) (B): Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd., "Aronix" is a registered trademark of the company)

[0098] (Photoinitiator) (C): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime) (Irgacure OXE-02, manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company)

[0099] (Carbon black dispersion) (D): Carbon black concentration 25.0 mass%, polymer dispersant concentration 5.0 mass%, dispersion resin (PGMEA dispersion of the alkali-soluble resin (A) in the synthesis example (solid content 5.0 mass%) (solid content 35.0 mass%))

[0100] (E): Silica PGMEA dispersion "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration 40 mass%, average particle diameter 50 nm)

[0101] (Solvent) (First solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (Second solvent) (F)-2: Cyclohexanone (ANON) (F)-3: Ethyl lactate (EL) (F)-4: 3-Methoxy-3-methylbutanol (MMB) (F)-5: Propylene glycol monomethyl ether (PGME) (Third solvent) (F)-6: Diethylene glycol dimethyl ether (MDM) (F)-7: Diethylene glycol ethyl methyl ether (EDM) (F)-8: Diethylene glycol diethyl ether (EDE) (F)-9: Diethylene glycol dibutyl ether (BDB)

[0102]

Table 1

[0103] [Table 2]

[0104] [Evaluation] A cured film (light-shielding film) obtained by curing a photosensitive resin composition for black resist used for evaluation was produced as follows.

[0105] (Preparation of cured film (light-shielding film) for foreign matter, optical density, and reflectance evaluation) The photosensitive resin compositions shown in Tables 1 and 2 were irradiated with ultraviolet light having an illuminance of 1000 mJ / cm at a wavelength of 254 nm using a low-pressure mercury lamp in advance to clean the surface, and then spin-coated on a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Inc.) (hereinafter referred to as "glass substrate") so that the film thickness after heat curing treatment would be 1.2 μm. A dry light-shielding film was produced by pre-baking at 90°C for 1 minute using a hot plate. Next, the entire surface of the dry light-shielding film was irradiated with ultraviolet light of 50 mJ / cm at an i-line illuminance of 30 mW / cm 2 using an ultra-high pressure mercury lamp to carry out the photocuring reaction of the light-shielding film. 2 2

[0106] Next, the exposed cured film (light-shielding film) was developed at a shower pressure of 1 kgf / cm for 1 minute with a 0.04% potassium hydroxide solution at 25°C, and then spray washed with water at 5 kgf / cm 2 2 . The developed light-shielding film was post-cured (post-baked) at 230°C for 30 minutes using a hot air dryer to obtain the cured films (light-shielding films) according to Examples 1 to 14 and Comparative Examples 1 to 8.

[0107] The cured films (light-shielding films) obtained by curing the photosensitive resin compositions for black resist of Examples 1 to 14 and Comparative Examples 1 to 8 obtained above were evaluated for the following items.

[0108] [Foreign matter evaluation] (Evaluation method) ​​​The cured film (light-shielding film) after this hardening (post-baking) was observed using a microscope to confirm the presence or absence of foreign matter derived from aggregates. Note that a result of △ or higher was considered qualified.

[0109] (Evaluation Criteria for Foreign Matter) ○: No foreign matter derived from aggregates was confirmed in the cured film (light-shielding film). △: Foreign matter derived from aggregates was confirmed in a part of the cured film (light-shielding film). ×: Foreign matter derived from aggregates was confirmed over the entire surface of the cured film (light-shielding film).

[0110] [Optical Density Evaluation] (Evaluation Method) Using a Macbeth transmission densitometer, the optical density (OD) of the fabricated cured film (light-shielding film) was evaluated. Also, the film thickness of the cured film (light-shielding film) formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was defined as OD / μm.

[0111] The optical density (OD) was calculated by the following formula (1). Optical density (OD) = -log 10 T(1) (T indicates the transmittance.)

[0112] [Reflectance Evaluation] (Evaluation Method) For the substrate with a light-shielding film fabricated in the same manner as the light-shielding film for optical density (OD) evaluation, the reflectance on the substrate (glass substrate) side at an incident angle of 2° was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0113] [Coating Unevenness Evaluation] (Evaluation Method) (Preparation of Cured Film (Light-Shielding Film) for Coating Unevenness Evaluation) The photosensitive resin composition shown in Tables 1 and 2 was irradiated with a low-pressure mercury lamp in advance at an illuminance of 1000 mJ / cm at a wavelength of 254 nm 2A 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Inc.) (hereinafter referred to as "glass substrate") whose surface was cleaned by irradiating with ultraviolet rays was coated using a spin coater so that the film thickness after heat curing treatment became 1.2 μm, vacuum dried at 200 Pa for 1 minute using a VCD, and pre-baked at 90 °C for 1 minute using a hot plate to produce a dry light-shielding film. Next, the obtained dry light-shielding film was post-baked at 230 °C for 30 minutes to obtain cured films (light-shielding films) according to Examples 1 to 14 and Comparative Examples 1 to 8.

[0114] (Evaluation method) The cured film (light-shielding film) after post-baking was visually observed to confirm the uniformity of the coating film. Note that a result of △ or more was considered to be qualified.

[0115] (Evaluation criteria for coating unevenness evaluation) ○: No unevenness was confirmed in the cured film (light-shielding film). △: Unevenness was confirmed in a part of the cured film (light-shielding film). ×: The cured film (light-shielding film) was not formed uniformly, and unevenness was confirmed over the entire surface.

[0116] The above evaluation results are shown in Tables 3 and 4.

[0117]

Table 3

[0118]

Table 4

[0119] As shown in Examples 1 to 14, by including a second solvent having a relative permittivity at 23°C of 10 to 30 and setting the relative permittivity of the entire solvent at 23°C to 8.5 or more, it was found that a light-shielding film having high light-shielding properties and low reflectance and suppressed generation of aggregates could be obtained. This is presumably because by setting the relative permittivity of the second solvent to 10 to 30 and the relative permittivity of the entire solvent to 8.5 or more at 23°C, the silanol groups remaining on the surface of the silica particles can be stabilized by solvation.

[0120] In particular, in Examples 1 to 3, 7 to 11, 13, and 14, which contain a second solvent having a relative permittivity at 23°C of 13 or more and the content of the second solvent relative to the mass of the total solvent is 20 to 50% by mass, the generation of aggregates as seen in Comparative Examples 4 to 8 was significantly suppressed, and no decrease in optical density was observed. This is presumably because the silanol groups on the surface of the silica particles were more effectively solvated by the second solvent having a high relative permittivity.

[0121] In Examples 9 to 14 containing a third solvent, in addition to the suppression of aggregates derived from silica particles as an effect of the second solvent, the drying property is also improved by the effect of the third solvent having a high boiling point, and coating unevenness can be suppressed.

Industrial Applicability

[0122] According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition for a black matrix that achieves both high light-shielding properties and low reflectance, a light-shielding film using the same, a color filter, and a touch panel. Further, according to this color filter and touch panel, it is possible to provide various display devices having excellent visibility.

Claims

【Claim 1】 (A) an unsaturated group-containing photosensitive resin; (B) a photopolymerizable monomer having at least two or more unsaturated bonds; (C) a photoinitiator; (D) at least one light-shielding component selected from a black pigment, a mixed-color pigment, and a light-shielding material; (E) silica particles; (F) a solvent; which contains the above as essential components, wherein the (F) solvent includes a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent having a relative dielectric constant at 23°C of 10 to 30; and a photosensitive resin composition for a black resist, characterized in that the relative dielectric constant at 23°C of the entire (F) solvent is 8.5 or more.

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