Photosensitive resin composition for black resist, light-shielding layer cured thereof, color filter and touch panel having that layer, and display device having them

Abstract

[Problem] To provide a photosensitive resin composition for black resist that has high light-blocking properties and low reflectivity, and is capable of suppressing the occurrence of aggregates. [Solution] The photosensitive resin composition for black resist of the invention comprises (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-blocking component selected from black pigment, mixed pigment and light-blocking material, (E) silica particles, and (F) a solvent.

Description

Technology Field

[0001] The present invention relates to a photosensitive resin composition for a 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 Technology

[0002] Recently, due to the development of mobile terminals, display devices such as touch panels and liquid crystal panels used outdoors or in vehicles are increasing. In the above display device, a light-blocking film is formed on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back, and a black matrix is ​​formed on the liquid crystal panel to suppress light leakage from the screen when displaying black and to suppress color mixing between adjacent color resists.

[0003] In order to improve the visibility of the screen of a display device, etc., by suppressing light leakage, etc., there are cases where the concentration of black pigment in the light-shielding film is increased to increase the light-shielding properties of the light-shielding film (lower the light transmittance of the light-shielding film). Since the refractive index of the black pigment is higher than that of the transparent substrate or the curable resin, if the concentration of black pigment in the light-shielding film is increased, the reflectance increases when viewed from the side opposite to the side on which the light-shielding film is formed on the transparent substrate. Consequently, reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and problems arise such as reflection on the light-shielding film or the black matrix boundary becoming noticeable due to the difference in reflectance with the colored part of the color filter.

[0004] For this reason, a photosensitive resin composition for black resist having both high light-blocking properties and low reflectivity, and a light-blocking film and color filter formed by curing the same are desired.

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition characterized by including hydrophobic silica particles and a specific dispersant (urethane-based dispersant). According to Patent Document 1, it is stated that by using hydrophobic silica particles and a specific dispersant, a black matrix capable of achieving both high light-blocking properties and low reflectivity can be formed. Prior art literature

[0006] (Patent Document 1) Japanese Patent Publication No. 2015-161815 The problem to be solved

[0007] However, as a result of the inventors' investigation, it was not possible to obtain a light-shielding film having both desired light-shielding properties and reflectivity in the black photosensitive resin composition described in Patent Document 1. In addition, in the black photosensitive resin composition described in Patent Document 1, aggregates originating from silica particles were generated, which sometimes caused light leakage in thickened areas or edges, or foreign matter in the openings.

[0008] Therefore, the inventors carefully examined the problem of conventional photosensitive resin compositions and found that silica particles have the characteristic of easily aggregating through silanol groups present on the particle surface, and generally, they are made dispersed in organic solvents by being coated with a silane coupling agent. However, it is difficult to coat all silanol groups present on the surface with a silane coupling agent, and when mixed with resin compositions of different polarities, the dispersion state becomes unstable and tends to aggregate. They discovered that by mixing a polar solvent with a high dielectric constant as a resist solvent within an appropriate range, the silanol groups on the surface of the silica particles can be stabilized by solvent coupling, and the aggregation of the silica particles can be suppressed.

[0009] The present invention is made in consideration of these points and aims to provide a photosensitive resin composition for a black resist having high light-blocking properties and low reflectivity and capable of suppressing the occurrence of aggregates, a light-blocking film formed by curing the same, a color filter and a touch panel having the light-blocking film, and a display device having the color filter and the touch panel. means of solving the problem

[0010] The photosensitive resin composition for black resist according to the present invention comprises (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two 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 as essential components, wherein the solvent (F) comprises a first solvent which is propylene glycol monomethyl ether acetate and a second solvent which has a relative permittivity of 10 to 30 at 23°C, and the relative permittivity of the entire solvent (F) at 23°C is 8.5 or higher.

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

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

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

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

[0015] According to the present invention, a photosensitive resin composition for a black resist capable of having high light-blocking properties and low reflectivity and suppressing the occurrence of aggregates, a light-blocking film formed by curing the same, a color filter and a touch panel having the light-blocking film, and a display device having the color filter and the touch panel can be provided. Specific details for implementing the invention

[0016] The present invention will be described in detail below. The photosensitive resin composition for black resist according to the present invention (hereinafter abbreviated as photosensitive resin composition) comprises (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two 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 as essential components. Components (A) to (F) will be described below.

[0017] 1. (A) Component

[0018] The photosensitive resin containing unsaturated groups, which is 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 carboxyl group. The above resin is not particularly limited and can be widely used.

[0019] Examples of the above-mentioned photosensitive resins containing unsaturated groups include epoxy (meth)acrylate acid adducts obtained by reacting (meth)acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter also referred to as "bisphenol-type epoxy compound represented by general formula (1)"), and reacting a polybasic carboxylic acid or its anhydride with the resulting compound having hydroxyl groups. An epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with an epihalohydrin or an equivalent thereof. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to either or both of these.

[0020] (A) The photosensitive resin containing unsaturated groups is preferably a photosensitive resin containing unsaturated groups obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by general formula (1) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride.

[0021]

[0022] (In formula (1), R1, R2, R3 and R4 are each independently one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond; and l is an integer from 0 to 10.)

[0023]

[0024] The bisphenol-type epoxy compound represented by general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. Since this reaction generally involves the oligomerization of diglycidyl ether compounds, it contains epoxy compounds containing two or more bisphenol backbones.

[0025] 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-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, Bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, 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, etc. are included. Among these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0026] In addition, examples of (a) acid monohydrides of dicarboxylic acids or tricarboxylic acids that are reacted with the hydroxyl groups in the epoxy(meth)acrylate molecules obtained by reacting such an epoxy compound with (meth)acrylic acid include acid monohydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monohydrides of alicyclic dicarboxylic acids or tricarboxylic acids, acid monohydrides of aromatic dicarboxylic acids or tricarboxylic acids, etc. Here, examples of acid monohydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monohydrides such as succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc. In addition, acid monohydrides of dicarboxylic or tricarboxylic acids to which any substituent has been introduced are included. In addition, examples of acid monohydrides of alicyclic dicarboxylic or tricarboxylic acids include acid monohydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norborneneindicarboxylic acid. In addition, acid monohydrides of dicarboxylic or tricarboxylic acids to which any substituent has been introduced are also included. In addition, examples of acid monohydrides of aromatic dicarboxylic or tricarboxylic acids include acid monohydrides such as phthalic acid, isophthalic acid, and trimellitic acid. In addition, acid monohydrides of dicarboxylic or tricarboxylic acids to which any substituent has been introduced are included.

[0027] In addition, as the acid dihydride of (b) a tetracarboxylic acid reacted with the epoxy(meth)acrylate, an acid dihydride of a chain hydrocarbon tetracarboxylic acid, an acid dihydride of a licyclic tetracarboxylic acid, or an acid dihydride of an aromatic tetracarboxylic acid is used. Here, examples of acid dihydrides of chain hydrocarbon tetracarboxylic acids include acid dihydrides of butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc. Additionally, acid dihydrides of tetracarboxylic acids to which any substituent has been introduced are included. In addition, examples of acid dihydrides of alicyclic tetracarboxylic acids include acid dihydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornenetetracarboxylic acid. In addition, acid dihydrides of tetracarboxylic acids to which any substituent has been introduced are included. In addition, examples of acid dihydrides of aromatic tetracarboxylic acids include acid dihydrides such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenylethertetracarboxylic acid. In addition, acid dihydrides of tetracarboxylic acids to which any substituent has been introduced are included.

[0028] The molar ratio (a) / (b) of (a) an acid anhydride of a dicarboxylic acid or tricarboxylic acid and (b) an acid dihydride of a tetracarboxylic acid reacted with epoxy(meth)acrylate is preferably 0.01 to 10.0, and more preferably 0.02 or higher and less than 3.0. If the molar ratio (a) / (b) deviates from the above range, it is undesirable because the optimal molecular weight for making a photosensitive resin composition with good patternability is not obtained. In addition, as the molar ratio (a) / (b) decreases, the molecular weight tends to increase and alkali solubility tends to decrease.

[0029] 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 a polybasic carboxylic acid or its acid anhydride, are not particularly limited, and known methods may be employed. Furthermore, the unsaturated group-containing photosensitive resin synthesized in the above reaction preferably has a weight average molecular weight (Mw) of 2000 to 10000 and an acid value of 30 to 200 mg / KOH.

[0030] Other examples of preferred resins as the unsaturated group-containing photosensitive resin of component (A) include a copolymer of (meth)acrylic acid, (meth)acrylic acid esters, etc., having (meth)acryloyl groups and carboxyl groups. Examples of the resins include a polymerizable unsaturated group-containing alkali-soluble resin obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting (meth)acrylic acid with the copolymer, and finally reacting an anhydride of a dicarboxylic acid or tricarboxylic acid. The above copolymer is a copolymer having a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mg KOH / g, comprising 20 to 90 mol% of repeating units derived from diesterglycerol in which hydroxyl groups at both ends are esterified with (meth)acrylic acid as disclosed in Japanese Patent Publication No. 2014-111722, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable with the same; and a polymerizable polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, comprising a unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di or tricarboxylic acid residue as disclosed in Japanese Patent Publication No. 2018-141968. Alkali-soluble resins containing unsaturated groups can be referenced.

[0031] (A) Regarding the photosensitive resin containing unsaturated groups, only one type may be used alone, or two or more types may be used in combination.

[0032] 2. (B) Component

[0033] Examples of photopolymerizable monomers having at least two or more unsaturated bonds in component (B) according to the present 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, trimethylol propane tri(meth)acrylate, trimethylol ethane 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. (Meta)acrylic acid esters such as dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and resinous polymers having (meth)acrylic groups as compounds having ethylenically double bonds are included. It is acceptable to use only one type of these monomers alone, or to use two or more types in combination. Furthermore, the photopolymerizable monomer having at least two ethylenically unsaturated bonds can perform the role of cross-linking molecules of the contained alkali-soluble resin, and in order to exhibit this function, it is preferable to use one having three or more unsaturated bonds. In addition, it is preferable that the acrylic equivalent, obtained by dividing the molecular weight of the monomer by the number of (meth)acrylic groups in one molecule, is 50 to 300, and it is more preferable that the acrylic equivalent is 80 to 200. Also, component (B) does not have free carboxyl groups.

[0034] Examples of dendritic polymers having (meth)acryloyl groups as compounds having unsaturated bonds that can be included in the composition as (B) components include dendritic polymers obtained by adding a polyvalent mercapto compound to a portion of the carbon-carbon double bonds in the (meth)acryloyl groups of a polyfunctional (meth)acrylate. Specifically, dendritic polymers obtained by reacting the (meth)acryloyl groups of a polyfunctional (meth)acrylate represented by general formula (3) with a polyvalent mercapto compound represented by general formula (4) are included.

[0035]

[0036] (In Equation (3), R5 is a hydrogen atom or a methyl group, and R6 is R7(OH) k It is the remaining portion in which n of the k hydroxyl groups have been donated to the ester bonds in the formula. R7 is a residue obtained by removing a hydroxyl group from a polyalcohol, a polyalcohol ether, or an ester of a polyalcohol ether and a hydroxylic acid. Preferred R7(OH) k As such, it is a polyalcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, a polyalcohol ether formed by linking multiple molecules of said polyalcohol through ether bonds via the dehydration condensation of alcohols, or an ester of said polyalcohol or polyalcohol ether with a hydroxy acid. k and n independently represent integers from 2 to 20, provided that k ≥ n.

[0037]

[0038] (In Equation (4), R8 is a single bond or a 2-6 valent hydrocarbon group with 1 to 6 carbon atoms, and m is 2 when R8 is a single bond, and is equal to the valence of R8 when R8 is a 2-6 valent group.)

[0039] Examples of polyfunctional (meth)acrylates represented by 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 in combination of two or more types.

[0040] Examples of polymercapto compounds represented by general formula (4) include trimethylolpropanetri(mercaptoacetate), trimethylolpropanetri(mercaptopropionate), pentaerythritoltetra(mercaptoacetate), pentaerythritoltri(mercaptoacetate), pentaerythritoltetra(mercaptopropionate), dipentaerythritolhexa(mercaptoacetate), dipentaerythritolhexa(mercaptopropionate), etc. These compounds may be used alone or in combination of two or more types.

[0041] The mixing ratio of component (A) and component (B) is preferably 30 / 70 to 90 / 10 by weight (A) / (B), and more preferably 60 / 40 to 80 / 20. If the mixing ratio of component (A) is 30 / 70 or higher, the cured product after photocuring is less likely to become soft, and furthermore, since the acid value of the coating film in the unexposed area is less likely to decrease, the decrease in solubility to the alkaline developer can be suppressed. Therefore, it is less likely for the problem of the pattern edge becoming jagged or not sharp to occur. In addition, if the mixing ratio of component (A) is 90 / 10 or lower, the proportion of photoreactive functional groups in the resin is sufficient, so the desired cross-linked structure can be formed. Also, since the acid value of the resin component is not excessively high, the solubility to the alkaline developer in the exposed area is less likely to increase, so the formed pattern becoming thinner than the target line width or pattern defects can be suppressed.

[0042] 3. (C) Component

[0043] Examples of (C) photopolymerization initiators according to the present embodiment include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, etc., benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, etc.; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; Nonimidazole compounds such as 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, etc.; 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, etc. 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, Halomethyl-S-triazine compounds such as 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine;O-acyloxime compounds such as ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-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)butane-1-onoxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazole-3-yl-O-acetyloxime; Sulfur compounds such as benzyldimethylketal, thioxantone, 2-chlorothioxantone, 2,4-diethylthioxantone, 2-methylthioxantone, and 2-isopropylthioxantone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylonitrile, benzoyl peroxide, and cumene pyrophosphate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine are included. These photopolymerization initiators may be used alone or in combination of two or more types.

[0044] Examples of O-acyloxime-based compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by general formulas (5) and (6). Among these compounds, when using a high concentration of a light-blocking component, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm. In addition, the term "photopolymerization initiator" as used in the present invention is used to include sensitizers.

[0045]

[0046] (Equation (5), R9, R 10 Each independently represents a C1-15 alkyl group, a C6-18 aryl group, a C7-20 arylalkyl group, or a C4-12 heterocyclic group, and R11 ...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 portion may include unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Additionally, the alkyl group may be any straight-chain, branched, or cyclic alkyl group.

[0047]

[0048] (In Equation (6), R 12 and R 13 Each is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, cycloalkylalkyl group, or alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms. 14 Each is independently a straight-chain or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a portion of the -CH2- group in the alkyl group or alkenyl group may be substituted with an -O- group. In addition, these R 12 ~R 14 Some of the hydrogen atoms in the gas may be replaced with halogen atoms.)

[0049] The amount of photopolymerization initiator of component (C) is preferably 3 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of each component of (A) and (B). When the mixing ratio of component (C) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization speed can be obtained. When the mixing ratio of component (C) is 30 parts by weight or less, appropriate sensitivity can be obtained, so a desired pattern line width and a desired pattern edge can be obtained.

[0050] 4. (D) Component

[0051] The light-blocking component (D) according to the present embodiment, such as a black pigment, a mixed pigment, and a light-blocking material, may be any known light-blocking component without special limitations as long as it is dispersed with an average particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction-scattering particle size distribution system or a dynamic light scattering particle size distribution system).

[0052] (D) Examples of black pigments that are components include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, etc.

[0053] (D) Examples of mixed pigments that are components include at least two colors mixed pigments selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, slen pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments.

[0054] Depending on the function of the photosensitive resin composition to be intended, the above (D) component may be used alone or two or more types may be used in combination.

[0055] In addition, examples of organic pigments that can be used when a mixed pigment is used as component (D) include, but are not limited to, those with the following numbers in color index name.

[0056] 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.

[0057] Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

[0058] 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.

[0059] Pigment Green 7, 36, 58, etc.

[0060] Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

[0061] Pigment Violet 19, 23, 37, etc.

[0062] Regarding the mixing ratio of the light-blocking component of component (D), it can be arbitrarily determined according to the desired degree of light blocking, but it is preferable that it be 20 to 80 mass% with respect to the solid content in the photosensitive resin composition, and more preferable that it be 40 to 70 mass%. When using organic pigments such as aniline black, cyanine black, lactam black, or carbon-based light-blocking components such as carbon black as the light-blocking component of component (D), it is particularly preferable that it be 40 to 60 mass% with respect to the solid content in the photosensitive resin composition. If the light-blocking component is 20 mass% or more with respect to the solid content in the photosensitive resin composition, sufficient light blocking can be obtained. If the light-blocking component is 80 mass% or less with respect to the solid content in the photosensitive resin composition, the content of the photosensitive resin that serves as the original binder does not decrease, so the desired developing characteristics and film-forming performance can be obtained.

[0063] The above component (D) is a light-blocking component dispersed in a solvent and is typically mixed with other components, at which time a dispersant may be added. The dispersant may be any known compound used for dispersing pigments (light-blocking components) (such as compounds commercially available under names such as dispersant, dispersion wetting agent, dispersion promoter, etc.) without any particular restrictions.

[0064] Examples of dispersants include cationic polymer-based dispersants, anionic polymer-based dispersants, nonionic polymer-based dispersants, and pigment derivative-type dispersants (dispersion aids). In particular, it is preferable that the dispersant be a cationic polymer-based dispersant having cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, and primary, secondary, or tertiary amino groups as adsorption sites for the coloring agent, with an amine value in the range of 1 to 100 mgKOH / g and a number average molecular weight (Mn) in the range of 1,000 to 100,000. The amount of this dispersant is preferably 1 to 35 mass% with respect to the light-blocking component, and more preferably 2 to 25 mass%. Furthermore, high-viscosity materials such as resins generally have a dispersion-stabilizing effect, but those that do not have dispersion-promoting ability are not treated as dispersants. However, their use for the purpose of stabilizing dispersion is not restricted.

[0065] 5. (E) Component

[0066] (E) The silica particles, which are the component, are not particularly limited in their manufacturing method, such as gas phase reaction or liquid phase reaction, or their shape (spherical, non-spherical).

[0067] The type of silica particles used as component (E) in the present invention is not particularly limited. Solid silica may be used, or hollow silica particles may be used. Furthermore, "hollow silica particles" refers to silica particles having a cavity inside the particle.

[0068] By using the above silica particles, the refractive index of the light-shielding film containing the above silica particles can be lowered.

[0069] The average particle diameter of the silica particles is preferably 1 to 100 nm, and more preferably 10 to 90 nm. Compared to cases where the average particle diameter is small, such as a few nm, it is considered that aggregation of silica particles is unlikely to occur within the above range. As a result, within the above particle diameter range, silica particles can exist uniformly within the light-shielding film because they exhibit excellent dispersion stability. Therefore, deviations in reflectance on the light-shielding film are unlikely to occur.

[0070] The average particle diameter of the above silica particles can be measured by the cumulant method using the dynamic light scattering particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Denshi Co., Ltd.).

[0071] In addition, the content of the silica particles is preferably 0.1 to 5 parts by mass relative to the total mass of the photosensitive resin composition, and more preferably 0.1 to 2 parts by mass. If the content of the silica particles is within the above range, good patternability can be ensured while achieving low reflectivity.

[0072] In addition, silica particles with a refractive index of 1.10 to 1.47 may be used. In addition to using conventional silica particles with a refractive index of 1.45 to 1.47, by using hollow silica particles with a low refractive index, the refractive index of the light-shielding film may be made lower than that of a light-shielding film containing only conventional silica particles.

[0073] In addition, the refractive index of the silica particles can be obtained from a transparent mixture obtained by mixing the silica particles, processed into a powder form, with a standard refractive index of known refractive index. In this case, the refractive index of the standard refractive index of the mixture is taken as the refractive index of the silica particles. Furthermore, the refractive index of the silica particles can be measured using an Abbe refractive index meter.

[0074] In addition, since reflection caused by the difference in refractive index between the transparent substrate and the light-blocking film formed can be suppressed, reflection can be suppressed without forming an anti-reflection film on a separate substrate.

[0075] The shape of the above silica particles may be spherical or elliptical. In the present invention, it is preferable that the shape of the silica particles used be spherical.

[0076] It is preferable that the silica particles have a sphericity of 1.0 to 1.5. When the sphericity of the silica particles is within this range, the particle shape becomes close to a sphere. Because of this, it is possible to homogeneously fill the thin light-shielding film, 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 smoothness of the film surface. Therefore, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0077] The sphericity of the above silica particles can be obtained from the ratio of the longest diameter to the shortest diameter of the particles (average value of 100 random silica particles). Here, the longest diameter and 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 shortest diameter of the silica particles from the obtained microscope image.

[0078] 6. (F) Component

[0079] (F) The solvent component comprises a first solvent which is propylene glycol monomethyl ether acetate and a second solvent which has a dielectric constant of 10 to 30 at 23°C.

[0080] (F) Among the solvents, the first solvent is propylene glycol monomethyl ether acetate. The content of the first solvent is preferably 10 to 90 mass% with respect to the total mass of the (F) component, and more preferably 20 to 80 mass%. By including 10 to 90 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.

[0081] In addition, the dielectric constant of the second solvent at 23°C is 10 to 30, and it is more preferable that it is 13 to 20. By using a solvent having a dielectric constant 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 silica particles in the resist composition can be suppressed.

[0082] The second solvent preferably comprises saturated ketones having a chain, branched, or cyclic structure having 3 to 12 carbon atoms, or saturated or unsaturated alcohols having a chain, branched, or cyclic structure having 3 to 12 carbon atoms.

[0083] Examples of the second solvents mentioned above include ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; alcohols such as ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and ethyl lactate; and glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-3-methylbutanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether.

[0084] The content of the second solvent is preferably 10 to 50 mass% with respect to the total mass of the solvent (F), more preferably 20 to 50 mass%, and even more preferably 25 to 50 mass%. By keeping the solvent content within the above range, good coating properties can be provided while suppressing the aggregation of silica particles.

[0085] In addition, the dielectric constant of the above (F) solvent can be measured using a dielectric constant meter “Model 871” (manufactured by Nippon Lufto Co., Ltd.).

[0086] In addition, (F) as a solvent, a third solvent having a boiling point of 150°C to 350°C at atmospheric pressure other than the first solvent and the second solvent may be included. It is preferable that the boiling point of the third solvent at atmospheric pressure be 150°C to 350°C, and more preferable that it be 160°C to 300°C.

[0087] In addition to the first solvent, propylene glycol monomethyl ether acetate, and the second solvent having a dielectric constant of 10 to 30 at 23°C, a third solvent having a boiling point of 150°C to 350°C at atmospheric pressure can be mixed and used.

[0088] Examples of the third solvent include acetic acid esters such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monoethyl ether acetate, and ethyl 3-ethoxypropionate; 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.

[0089] The content of the third solvent is preferably 1 to 30 mass% and preferably 1 to 20 mass% with respect to the total mass of the solvent (F). By including the third solvent in the range of 1 to 30 mass%, the aggregation of silica particles can be suppressed. In addition, the drying properties of the resist can be controlled, and the occurrence of drying foreign matter in the dolby or coater nozzle during vacuum drying can be suppressed.

[0090] In addition, the dielectric constant of the entire solvent (F) at 23°C is preferably 8.5 or higher and 15.0 or lower, and more preferably 8.8 or higher and 15.0 or lower. By making the dielectric constant of the entire solvent (F) at 23°C 8.5 or higher, the silanol groups remaining on the surface of the silica particles can be stabilized by solvation, and the aggregation of the silica particles can be suppressed. In addition, by making the dielectric constant at 23°C 15.0 or lower, good drying performance and coating performance can be ensured in the VCD process of drying the solvent under reduced pressure. Here, "entire solvent" refers to a mixed solvent of the first solvent and the second solvent, or a mixed solvent of the first solvent, the second solvent, and the third solvent.

[0091] In addition, the photosensitive resin composition of the present invention may, if necessary, incorporate additives such as a resin other than component (A), such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler other than silica, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent.

[0092] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindard phenolic compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0093] The photosensitive resin composition of the present invention preferably comprises, in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid after photocuring), (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from black pigment, mixed pigment, and light-shielding material, and (E) silica particles. The amount of solvent varies depending on the target viscosity, but is preferably 40 to 90 mass% of the total amount.

[0094] In addition, a light-blocking film formed by curing the photosensitive resin composition of the present invention is obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent, and curing it by irradiating it with light (including ultraviolet rays, radiation, etc.). By using a photomask or the like to form areas exposed to light and areas not exposed to light, curing only the areas exposed to light, and dissolving the other areas with an alkaline solution, a desired pattern is obtained.

[0095] In addition, a color filter or touch panel having the light-shielding film of the present invention as a black matrix is ​​manufactured by, for example, forming a light-shielding film having a film thickness of 1.0 to 2.0 μm on a transparent substrate, forming each of red, blue, and green pixels by photolithography after forming the light-shielding film, and also embedding red, blue, and green inks into the light-shielding film using an inkjet process.

[0096] In addition, the light-shielding film formed by curing the photosensitive resin composition of the present invention may also be used as a black column spacer for a liquid crystal display device. For example, multiple sections with different film thicknesses may be produced using a single black resist, with one section functioning as a spacer and the other as a black matrix.

[0097] Each process of the method for forming a light-blocking film by applying and drying a photosensitive resin composition is specifically exemplified.

[0098] As a method for applying a photosensitive resin composition to a substrate, any of the known methods such as solution immersion, spraying, using a roller coater, a land coater, a slit coater, or a spinner may be employed. After applying to a desired thickness by these methods, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time during pre-baking can be appropriately selected depending on the solvent used, but for example, it is preferable to perform it at 80 to 120°C for 1 to 10 minutes.

[0099] As radiation used for exposure, for example, visible light, ultraviolet light, far-ultraviolet light, electron beams, X-rays, etc., may be used, but the wavelength range of the radiation is preferably 250 to 450 nm. In addition, as a developer suitable for this alkaline development, aqueous solutions of, for example, sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc., may be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using commercially available developers or ultrasonic cleaners. In addition, the surface is typically rinsed with water after alkaline development. As development methods, shower development, spray development, dip development, puddle development, etc., can be applied.

[0100] After developing in this manner, heat treatment (post-baking) is performed at 180 to 250°C for 20 to 100 minutes. This post-baking is performed for purposes such as increasing the adhesion between the patterned cured film (light-shielding film) and the substrate. Similar to pre-baking, this is performed by heating with an oven, a hot plate, etc. The patterned cured film (light-shielding film) of the present invention is formed by undergoing each process by photolithography. Then, polymerization or curing (the two may be collectively referred to as curing) is completed by heat, thereby obtaining a light-shielding film having a desired pattern.

[0101] The photosensitive resin composition for black resist of the present invention is not only suitable for forming fine patterns by operations such as exposure and alkali development as described above, but also allows for obtaining a light-shielding film with excellent light-shielding properties, adhesion, electrical insulation, heat resistance, and chemical resistance even when a pattern is formed by conventional screen printing.

[0102] The photosensitive resin composition for black resist according to the present invention can be suitably used as a coating material. In particular, the color filter ink used in liquid crystal display devices or imaging elements, and the light-blocking film formed by it, are useful as color filters, black matrices for liquid crystal projection, etc. Furthermore, the photosensitive resin composition for black resist according to the present invention can be used as an ink material for color fractionation or light-blocking in various multi-color display devices, such as organic electroluminescent devices represented by organic EL elements, color liquid crystal display devices, color facsimiles, and image sensors, in addition to color filter ink for color liquid crystal displays. According to the color filter of the present invention, the reflection of external light at the interface between the coloring layer (including the black resist layer) and the substrate, or, for example, the reflection of light emission from the element when used in an organic EL element, can be reduced. That is, it is possible to realize an improvement in spot contrast by reducing the reflection of external light, or an improvement in luminous efficiency by improving the light extraction efficiency from the light-emitting side.

[0103] (Example)

[0104] The embodiments of the present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these.

[0105] First, the synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin, which is component (A), will be described. Unless otherwise noted, the evaluation of the resins in these synthesis examples was performed as follows.

[0106] [Solid content concentration]

[0107] 1 g of the resin solution obtained from 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 calculated from the following formula.

[0108] Solid content concentration (weight%) = 100 × (W2 - W0) / (W1 - W0)

[0109] [Sanga]

[0110] The resin solution was dissolved in dioxane, and the result was obtained by titrating with a 1 / 10 N-KOH aqueous solution using the potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0111] [Molecular weight]

[0112] The weight average molecular weight (Mw) was calculated using gel permeation chromatography (GPC) “HLC-8220GPC” (Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2)+TSKgelSuperH-3000 (1)+TSKgelSuperH-4000 (1)+TSKgelSuperH-5000 (1) (Tosoh Co., Ltd.), temperature: 40℃, rate: 0.6 ml / min), and the weight average molecular weight was calculated as a converted value of standard polystyrene (Tosoh Co., Ltd., PS-oligomer kit).

[0113] [Average particle diameter]

[0114] The average particle diameter of the silica particles was determined by the cumulant method using the dynamic light scattering particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Denshi Co., Ltd.).

[0115] The abbreviations used in the synthetic examples and comparative synthetic examples are as follows.

[0116] BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxylan. A compound of general formula (1), wherein X is a fluorene-9,9-diyl group and R1 to R4 are hydrogen compounds.

[0117] AA: Acrylic acid

[0118] BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

[0119] THPA: Tetrahydrophthalic anhydride

[0120] TEAB: Tetraethylammonium bromide

[0121] PGMEA: Propylene glycol monomethyl ether acetate

[0122] [Synthetic Example]

[0123] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were added to a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100–105°C for 20 hours. Subsequently, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask and stirred at 120–125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A). The solid content of the obtained resin solution was 56.1 mass%, the acid value (converted to solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[0124] Photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were prepared using the blending amounts (units are mass%) listed in Table 1. The blending components used in the table are as follows.

[0125] (Polymerizable alkali-soluble resin containing unsaturated groups)

[0126] (A): Alkali-soluble resin solution obtained in the above synthesis example (solid content concentration 56.1 mass%)

[0127] (Photopolymerizable monomer)

[0128] (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Doagosei Co., Ltd., “Aronix” is a registered trademark of the company)

[0129] (Photopolymerization initiator)

[0130] (C): Ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime)(IrgacureOXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of the company)

[0131] (Carbon black dispersion)

[0132] (D): Carbon black concentration 25.0 mass%, polymer dispersant concentration 5.0 mass%, dispersion resin (PGMEA dispersion of alkali-soluble resin (A) of the synthesis example (solid content 5.0 mass%) (solid content 35.0 mass%)

[0133] (E): Silica PGMEA dispersion "YA050C" (manufactured by Admatech, Inc., solid content 40 mass%, average particle diameter 50 nm)

[0134] (solvent)

[0135] (First Solvent)

[0136] (F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0137] (Second Solvent)

[0138] (F)-2: Cyclohexanone (ANON)

[0139] (F)-3: Ethyl lactic acid (EL)

[0140] (F)-4: 3-methoxy-3-methylbutanol (MMB)

[0141] (F)-5: Propylene glycol monomethyl ether (PGME)

[0142] (Solvent No. 3)

[0143] (F)-6: Diethylene glycol dimethyl ether (MDM)

[0144] (F)-7: Diethylene glycol ethylmethyl ether (EDM)

[0145] (F)-8: Diethylene glycol diethyl ether (EDE)

[0146] (F)-9: Diethylene glycol dibutyl ether (BDB)

[0147]

[0148] [evaluation]

[0149] A cured film (light-blocking film) formed by curing a photosensitive resin composition for black resist to be used for evaluation was prepared as follows.

[0150] (Preparation of a hardened film (light-blocking film) for evaluating foreign substances, optical density, and reflectance)

[0151] A photosensitive resin composition shown in Table 1 was applied using a spin coater to a 125 mm × 125 mm glass substrate “#1737” (manufactured by Corning, hereinafter referred to as the “glass substrate”), the surface of which had been cleaned by irradiating it with ultraviolet light of 1000 mJ / cm² with a wavelength of 254 nm using a low-pressure mercury lamp, so that the film thickness after heat curing treatment was 1.2 μm, and a dried light-shielding film was produced by pre-baking it at 90°C for 1 minute using a hot plate. Subsequently, ultraviolet light of 50 mJ / cm² was irradiated onto the front surface of the dried light-shielding film using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm² to perform a photocuring reaction of the light-shielding film.

[0152] Next, the exposed cured film (light-blocking film) was developed for 1 minute at a shower pressure of 1 kgf / ㎠ using a 0.04% potassium hydroxide solution at 25°C, then spray-washed with water at 5 kgf / ㎠, and the developed light-blocking film was post-baked at 230°C for 30 minutes using a hot air dryer to obtain the cured films (light-blocking films) according to Examples 1 to 14 and Comparative Examples 1 to 8.

[0153] The cured film (light-blocking film) formed by curing the photosensitive resin composition for black resist of Examples 1 to 14 and Comparative Examples 1 to 8 obtained above was evaluated for the following items.

[0154] [Foreign Matter Evaluation]

[0155] (Evaluation Method)

[0156] The cured film (light-blocking film) after post-baking was observed using a microscope to check for the presence of foreign matter originating from aggregates. Additionally, a result of △ or higher was deemed acceptable.

[0157] (Evaluation criteria for foreign substance assessment)

[0158] ○: No foreign matter originating from aggregates is found on the hardened film (light-blocking film).

[0159] △: Foreign matter originating from aggregates is identified in a part of the hardened film (shading film).

[0160] ×: Foreign matter originating from aggregates is identified on the front surface of the hardened film (shading film).

[0161] [Optical Density Evaluation]

[0162] (Evaluation Method)

[0163] The optical density (OD) of the fabricated cured film (light-blocking film) was evaluated using a Macbeth transmission densitometer. In addition, the film thickness of the cured film (light-blocking film) formed on the substrate was measured, and the value obtained by dividing the optical density (OD) by the film thickness was defined as OD / μm.

[0164] The optical density (OD) was calculated using the following equation (1).

[0165] Optical density (OD) = -log10T (1)

[0166] (T represents transmittance)

[0167] [Reflectivity Evaluation]

[0168] (Evaluation Method)

[0169] For a substrate with a cured film (light-blocking film) attached, prepared in the same manner as the cured film (light-blocking film) for optical density (OD) evaluation, the reflectance on the substrate (glass substrate) side was measured at an incident angle of 2° using the ultraviolet-visible-infrared spectrophotometer “UH4150” (manufactured by Hitachi High-Tech Science Co., Ltd.).

[0170] [Evaluation of Non-uniformity of Coating]

[0171] (Evaluation Method)

[0172] (Preparation of a cured film (light-blocking film) for evaluating coating non-uniformity)

[0173] A photosensitive resin composition shown in Table 1 was applied using a spin coater to a 125 mm × 125 mm glass substrate “#1737” (manufactured by Corning, Inc.) (hereinafter referred to as the “glass substrate”), the surface of which had been cleaned by irradiating it with ultraviolet light of 1000 mJ / cm² with a wavelength of 254 nm using a low-pressure mercury lamp, so that the film thickness after heat curing treatment was 1.2 μm. The substrate was then 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 dried light-shielding film. Subsequently, the obtained dried light-shielding film was post-baked at 230°C for 30 minutes to obtain a cured film (light-shielding film) according to Examples 1 to 14 and Comparative Examples 1 to 8.

[0174] (Evaluation Method)

[0175] The cured film (light-blocking film) after post-baking was visually observed, and the uniformity of the film was confirmed. In addition, a rating of △ or higher was considered acceptable.

[0176] (Evaluation criteria for non-uniform coating)

[0177] ○: No non-uniformity is observed in the hardened film (light-blocking film).

[0178] △: Non-uniformity is observed in a part of the hardened film (shading film).

[0179] ×: The hardened film (light-blocking film) is not uniformly formed, and unevenness is observed on the front surface.

[0180] The above evaluation results are shown in Table 2.

[0181]

[0182] As shown in Examples 1 to 14, it was found that a light-blocking film having high light-blocking properties and low reflectivity, and suppressing the generation of aggregates, can be obtained by including a second solvent having a relative permittivity of 10 to 30 at 23°C and making the relative permittivity of the entire solvent at 23°C 8.5 or higher. This is thought to be because the silanol groups remaining on the surface of the silica particles can be stabilized by solvation by making the relative permittivity of the second solvent 10 to 30 and the relative permittivity of the entire solvent 8.5 or higher at 23°C.

[0183] In particular, in Examples 1 to 3, 7 to 11, 13, and 14, which include a second solvent having a dielectric constant of 13 or higher at 23°C and have a content of the second solvent of 20 to 50 mass% relative to the total mass of the solvent, the occurrence of aggregates as seen in Comparative Examples 4 to 8 was significantly suppressed, and no decrease in optical concentration was observed. This is thought to be because the silanol groups on the surface of the silica particles were more effectively solvated by the second solvent with a high dielectric constant.

[0184] In Examples 9 to 14 containing the third solvent, in addition to the effect of the second solvent which suppresses aggregates derived from silica particles, the effect of the third solvent which has a high boiling point also improves drying properties and makes it possible to suppress uneven coating.

[0185] (Industrial Applicability)

[0186] 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-blocking properties and low reflectivity, as well as a light-blocking film, a color filter, and a touch panel using the same. Furthermore, according to the color filter and touch panel, various display devices with excellent visibility can be provided.

Claims

Claim 1 A photosensitive resin composition for black resist, comprising (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two 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 as essential components, wherein the solvent (F) comprises a first solvent which is propylene glycol monomethyl ether acetate and a second solvent which is ethyl lactate or 3-methoxy-3-methylbutanol having a relative dielectric constant of 10 to 30 at 23°C, and wherein the relative dielectric constant of the entire solvent (F) at 23°C is 8.5 or higher. Claim 2 delete Claim 3 A photosensitive resin composition for a black resist, wherein the (A) unsaturated group-containing photosensitive resin is a photosensitive resin containing an unsaturated group obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by general formula (1) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. (In formula (1), R1, R2, R3 and R4 are each independently one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond; and l is an integer from 0 to 10.) Claim 4 delete Claim 5 delete Claim 6 A light-shielding film formed by curing a photosensitive resin composition for black resist described in claim 1. Claim 7 A color filter having the light-blocking film described in claim 6 as a black matrix. Claim 8 A touch panel having the light-blocking film described in claim 6 as a black matrix. Claim 9 A display device having a color filter as described in claim 7.

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