Photosensitive resin composition for black resist, method for producing said photosensitive resin composition, light-shielding film obtained by curing said photosensitive resin composition, color filter and touch panel having said light-shielding film, and display device having said color filter and touch panel

Abstract

To provide a photosensitive resin composition for black resist which has high light-shielding properties and low reflectance and is capable of forming a high-definition pattern.SOLUTION: The photosensitive resin composition for black resist according to the present invention contains: (A) an unsaturated group-containing photosensitive resin; (B) a photopolymerizable monomer having at least two unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material; (E) silica particles; and (F) a phosphate ester-based dispersant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition for black resist, a method for producing the photosensitive resin composition, a light-shielding film obtained by curing the photosensitive resin 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. [Background technology]

[0002] In recent years, the development of mobile terminals has led to an increase in display devices such as touch panels and liquid crystal panels for use outdoors or in vehicles. In these display devices, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back, and a black matrix is ​​provided 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 display devices and the like, in order to suppress light leakage and improve the visibility of the screen of the display device, the concentration of black pigment in the light-shielding film is sometimes increased to increase the light-shielding properties of the light-shielding film (reducing the light transmittance of the light-shielding film). Because the refractive index of the black pigment is higher than that of the transparent substrate and the curable resin, increasing the concentration of black pigment in the light-shielding film increases the reflectance when viewed from the side of the transparent substrate opposite the side on which the light-shielding film is formed. This increases the reflection at the interface between the transparent substrate and the light-shielding film formed on it, causing problems such as reflections on the light-shielding film and the black matrix boundary becoming more noticeable due to the difference in reflectance with the colored portion of the color filter.

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

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition containing hydrophobic silica particles and a specific dispersant (urethane-based dispersant). It is said that the use of the hydrophobic silica particles and the specific dispersant enables the formation of a black matrix that achieves both high light-shielding properties and low reflectance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-161815 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the inventors of the present invention have conducted studies and found that a light-shielding film having both the desired light-shielding properties and reflectance could not be obtained using the black photosensitive resin composition described in Patent Document 1. Furthermore, when the black photosensitive resin composition described in Patent Document 1 was used, jagged edges were sometimes formed on the pattern edges during pattern formation, and residues derived from silica particles were sometimes left on the substrate.

[0008] The present invention has been made in view of the above points, and an object of the present invention is to provide a photosensitive resin composition for black resist that has high light-shielding properties and low reflectance and is capable of forming high-resolution patterns, a light-shielding film obtained by curing the composition, a color filter and touch panel that have the light-shielding film, and a display device that has the color filter and touch panel. [Means for solving the problem]

[0009] The photosensitive resin composition for black resist according to the present invention comprises (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material, (E) silica particles, and (F) a phosphate ester-based dispersant.

[0010] The method for producing a photosensitive resin composition for a black resist according to the present invention comprises mixing (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component dispersion in which a light-shielding component is dispersed in a solvent, and (E) a silica particle dispersion in which silica particles are dispersed in a solvent, wherein the (E) silica particle dispersion contains (F) a phosphate ester-based dispersant.

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

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

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

[0014] A display device according to the present invention includes the color filter or the touch panel. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photosensitive resin composition for black resist, which has high light-shielding properties and low reflectance and is capable of forming a high-resolution pattern, 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. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below. The photosensitive resin composition for black resist of the present invention (hereinafter referred to as photosensitive resin composition) contains (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material, (E) silica particles, and (F) a phosphate ester-based dispersant. Components (A) to (F) will be described below.

[0017] 1. (A) Component The unsaturated group-containing photosensitive resin (A) according to the present embodiment preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably has both a polymerizable unsaturated group and a carboxyl group. The above resins can be widely used without any particular limitations.

[0018] An example of the unsaturated group-containing photosensitive resin is an epoxy (meth)acrylate acid adduct obtained by reacting an epoxy compound having two glycidyl ether groups derived from a bisphenol (hereinafter also referred to as a "bisphenol-type epoxy compound represented by 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 a bisphenol refers to an epoxy compound obtained by reacting a bisphenol with an epihalohydrin, or an equivalent thereof. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to either or both of these.

[0019] The unsaturated group-containing photosensitive resin (A) is preferably a bisphenol-type epoxy compound represented by general formula (1). By using the bisphenol-type epoxy compound represented by general formula (1), good development properties can be obtained.

[0020] [ka]

[0021] (In formula (1), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom; X represents -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 1 represents an integer of 0 to 10.)

[0022] [ka]

[0023] The bisphenol epoxy compound represented by general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore contains an epoxy compound having two or more bisphenol skeletons.

[0024] 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-hydroxyphenyl) ketone ... 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)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 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.

[0025] Examples of (a) dicarboxylic or tricarboxylic acid monoanhydrides that can be reacted with hydroxy groups in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include acid monoanhydrides of open-chain hydrocarbon dicarboxylic or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic or tricarboxylic acids. Examples of open-chain hydrocarbon dicarboxylic or tricarboxylic acid monoanhydrides include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Furthermore, acid monoanhydrides of dicarboxylic or tricarboxylic acids into which any substituent has been introduced are also included. Examples of acid monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. They also include acid monoanhydrides of dicarboxylic or tricarboxylic acids into which any substituent has been introduced. Examples of acid monoanhydrides of aromatic dicarboxylic or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, and trimellitic acid. They also include acid monoanhydrides of dicarboxylic or tricarboxylic acids into which any substituent has been introduced.

[0026] Furthermore, as the (b) tetracarboxylic acid dianhydride to be reacted with the 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. Examples of the acid dianhydride of a chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like. Furthermore, the acid dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein is also included. Examples of the acid dianhydride of an alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like. Further, the acid dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein is also included. Examples of the acid dianhydride of an aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. Further, the acid dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein is also included.

[0027] The molar ratio (a) / (b) of (a) dicarboxylic or tricarboxylic acid monoanhydride to (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate is preferably 0.01 or more and 10.0 or less, and more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight for obtaining a photosensitive resin composition with good photopatterning properties cannot be obtained, which is undesirable. Note that the smaller the molar ratio (a) / (b), the larger the molecular weight and the lower the alkali solubility.

[0028] The reaction between the epoxy compound and (meth)acrylic acid, and the reaction between the epoxy (meth)acrylate obtained by this reaction and a polybasic carboxylic acid or its acid anhydride, are not particularly limited, and known methods can be used. The unsaturated group-containing photosensitive resin synthesized by the above reaction preferably has a weight-average molecular weight (Mw) of 2,000 to 10,000 and an acid value of 30 to 200 mg / KOH. The weight-average molecular weight (Mw) can be measured, for example, using a gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). The acid value can be measured, for example, by titration with a 1 / 10 N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0029] Another example of a resin preferred as the unsaturated group-containing photosensitive resin (A) is a copolymer of (meth)acrylic acid, (meth)acrylic acid esters, etc., and includes a resin having a (meth)acryloyl group and a carboxy group. Examples of the resin include a polymerizable unsaturated group-containing alkali-soluble resin obtained by copolymerizing a (meth)acrylic acid ester containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymer include a copolymer disclosed in Japanese Patent Application Laid-Open No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and which has a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH / g; and a polymerizable unsaturated group-containing alkali-soluble resin disclosed in Japanese Patent Application Laid-Open No. 2018-141968, which is a polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, and which includes units derived from (meth)acrylic acid ester compounds and units having a (meth)acryloyl group and a di- or tricarboxylic acid residue.

[0030] The unsaturated group-containing photosensitive resin of the component (A) may be used alone or in combination of two or more types.

[0031] 2.(B) Component Examples of the photopolymerizable monomer having at least two or more unsaturated bonds in the 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 ... Examples of suitable photopolymerizable monomers include (meth)acrylic acid esters such as sorbitol 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and compounds having an ethylenic double bond, such as dendritic polymers having a (meth)acrylic group. One of these monomers may be used alone, or two or more may be used in combination. Furthermore, the photopolymerizable monomer having at least two ethylenically unsaturated bonds can serve to crosslink molecules of the alkali-soluble resin containing a polymerizable unsaturated group. To achieve this function, it is preferable to use a monomer having three or more unsaturated bonds. Furthermore, the acrylic equivalent, calculated by dividing the molecular weight of the monomer by the number of (meth)acrylic groups in one molecule, is preferably 50 to 300, and more preferably 80 to 200. Note that component (B) does not have a free carboxy group.

[0032] Examples of dendritic polymers having (meth)acryloyl groups as compounds having unsaturated bonds that can be contained in the composition as component (B) include dendritic polymers obtained by adding a polyvalent mercapto compound to part of the carbon-carbon double bonds in the (meth)acryloyl groups of a polyfunctional (meth)acrylate. Specific examples include 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).

[0033] [ka]

[0034] (In formula (3), R5 is a hydrogen atom or a methyl group, and R6 is R7(OH) k The remaining portion is obtained by donating n hydroxy groups out of k hydroxy groups to the ester bond in the formula. Preferred R7(OH) k is a polyhydric alcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking multiple molecules of the polyhydric alcohol via ether bonds by dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. k and n independently represent integers of 2 to 20, provided that k≧n.

[0035] [ka]

[0036] (In formula (4), R8 is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, and m is 2 when R8 is a single bond, and is the same as the valence of R8 when R8 is a divalent to hexavalent group.)

[0037] 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.

[0038] Examples of polyvalent mercapto compounds represented by general formula (4) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. These compounds may be used alone or in combination of two or more.

[0039] The blending ratio of component (A) to component (B), expressed as a weight ratio (A) / (B), is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20. When the blending ratio of component (A) is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to decrease in the unexposed areas, thereby suppressing a decrease in solubility in alkaline developers. This reduces the likelihood of problems such as jagged or dull pattern edges. Furthermore, when the blending ratio of component (A) is 90 / 10 or less, the proportion of photoreactive functional groups in the resin is sufficient, allowing the formation of the desired crosslinked structure. Furthermore, since the acid value of the resin component is not too high, the solubility in alkaline developers in the exposed areas is less likely to increase, thereby preventing the formed pattern from being thinner than the target line width or from being missing.

[0040] 3.(C) Component Examples of the photopolymerization initiator (C) according to this embodiment include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzoin ethers such as benzoin ether; biimidazole 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, and 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-siadiazole), and halomethylthiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 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, halomethyl-S-triazine compounds such as 2-(4-methylthiostyryl)-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, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine;O-acyloxime compounds such as 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; benzil dimethyl ketal, thioxanthone, Examples of suitable photopolymerization initiators include sulfur compounds such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination.

[0041] Examples of O-acyloxime compounds that can be preferably used include O-acyloxime photopolymerization initiators 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-acyloxime photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 or more. In the present invention, the term "photopolymerization initiator" is used to include a sensitizer.

[0042] [ka]

[0043] (In formula (5), R9, R 10each 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; 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 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 contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be a straight-chain, branched, or cyclic alkyl group.

[0044] [ka]

[0045] (In formula (6), R 12 and R 13 R are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 14 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. 12 ~R 14 A part of the hydrogen atoms in the group may be substituted with halogen atoms.

[0046] The amount of the photopolymerization initiator (C) used 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 components (A) and (B). When the blending ratio of component (C) is 3 parts by weight or more, good sensitivity can be achieved and a sufficient photopolymerization rate can be obtained. When the blending ratio of component (C) is 30 parts by weight or less, appropriate sensitivity can be achieved, allowing the desired pattern line width and desired pattern edge to be obtained.

[0047] 4.(D) Component The light-shielding components such as black pigments, mixed-color organic pigments, and light-shielding materials that are component (D) according to the present embodiment can be any known light-shielding component without any particular restrictions, as long as they are dispersed with an average particle size of 1 to 1,000 nm (average particle size measured with a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter).

[0048] Examples of black pigments as component (D) include perylene black, cyanine black, aniline black, lactam black, carbon black, and titanium black.

[0049] Examples of the mixed-color organic pigment that is component (D) include a pigment in which at least two colors are mixed and 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.

[0050] The component (D) may be used alone or in combination of two or more types depending on the desired function of the photosensitive resin composition.

[0051] Examples of organic pigments that can be used when a mixed color organic pigment is used as component (D) include, but are not limited to, those with the following color index numbers: 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.

[0052] The blending ratio of the light-shielding component (D) can be determined arbitrarily depending on the desired light-shielding degree, but is preferably 20 to 80 mass % and more preferably 40 to 70 mass % based on the solid content of the photosensitive resin composition. When an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black, is used as the light-shielding component (D), the blending ratio is particularly preferably 40 to 60 mass % based on the solid content of the photosensitive resin composition. When the light-shielding component is 20 mass % or more based on the solid content of the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light-shielding component is 80 mass % or less based on the solid content of the photosensitive resin composition, the content of the photosensitive resin, which originally serves as a binder, is not reduced, thereby achieving desired development characteristics and film-forming ability.

[0053] The component (D) is usually dispersed in a solvent to form a light-shielding component dispersion, which is then mixed with other formulation components, and a dispersant may be added at this time. The dispersant may be any known compound used to disperse pigments (light-shielding components) (e.g., compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion promoters, etc.) and the like, without any particular limitation.

[0054] Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing aids). In particular, the dispersant is preferably a cationic polymer dispersant having a cationic functional group, such as an imidazolyl group, a pyrrolyl group, a pyridyl group, or a primary, secondary, or tertiary amino group, as an adsorption site for the colorant, an amine value of 1 to 100 mgKOH / g, and a number-average molecular weight (Mn) of 1,000 to 100,000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, of the light-blocking component. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those without dispersion-promoting properties are not considered dispersants. However, this does not limit their use for the purpose of stabilizing dispersion.

[0055] In addition, the total mass (m D ) relative to the mass (m E ) ratio (m E / m D (D) The total mass (m D ) to (E) the mass of silica particles (m E When the ratio of (a) is within the above range, it is possible to achieve both high light blocking properties and low reflectance.

[0056] 5.(E) Component The silica particles, which are component (E), are not particularly limited in terms of the manufacturing method (gas phase reaction or liquid phase reaction) or the shape (spherical or non-spherical).

[0057] The type of silica particles used as component (E) in the present invention is not particularly limited. Solid silica or hollow silica particles may be used. Note that "hollow silica particles" refer to silica particles having a cavity inside the particle.

[0058] By using the silica particles, the refractive index of the light-shielding film containing the silica particles can be reduced.

[0059] The average particle size of the silica particles is preferably 1 to 100 nm, more preferably 10 to 90 nm. Compared to small particle sizes, such as a few nm, silica particles within this range are less likely to aggregate. Therefore, within this particle size range, silica particles have excellent dispersion stability and can be uniformly present within the light-shielding film. Therefore, variations in reflectance on the light-shielding film are less likely to occur.

[0060] The content of the silica particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, low reflectance can be achieved while good patterning properties can be ensured.

[0061] The average particle size of the silica particles can be measured by the cumulant method using a particle size distribution analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) that uses a dynamic light scattering method.

[0062] The refractive index of the silica particles can be 1.10 to 1.47. In addition to being able to use ordinary silica particles with a refractive index of 1.45 to 1.47, the use of hollow silica particles with a low refractive index can also make the refractive index of the light-shielding film lower than the refractive index of a light-shielding film containing only ordinary silica particles.

[0063] The refractive index of the silica particles can be determined from a transparent mixture obtained by mixing the powdered silica particles with a standard refractive index liquid having a known refractive index. In this case, the refractive index of the standard refractive index liquid in the mixture is taken as the refractive index of the silica particles. The refractive index of the silica particles can be measured using an Abbe refractometer.

[0064] Furthermore, since reflection caused by the difference in refractive index between the transparent substrate and the light-shielding film formed thereon can be suppressed, reflection can be suppressed without providing a separate anti-reflection film or the like on the substrate.

[0065] The silica particles may have a spherical or ellipsoidal shape, but the silica particles used in the present invention are preferably spherical.

[0066] The silica particles preferably 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 perfect sphere. This allows the particles to be uniformly filled in a 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 film surface smoothness. This allows a light-shielding film to be obtained that has a low refractive index and sufficient strength.

[0067] The sphericity of the silica particles can be determined from the ratio of the longest diameter to the shortest diameter (average value of 100 arbitrary silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values ​​determined 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.

[0068] The silica particles (component (E)) can be dispersed in a solvent to form a silica particle dispersion, which can be mixed with other formulation components. The dispersant can be any known compound (compounds commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) used for dispersing pigments (light-blocking components) without any particular restrictions. In this embodiment, the dispersant contained in the silica particle dispersion preferably includes a phosphate ester-based dispersant (F) (described below).

[0069] 6. (F) Component Examples of the (F) phosphate ester-based dispersant according to this embodiment include polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate monoesters, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate diesters, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate triesters, alkyl phosphate esters, alkyl ether phosphate esters, or derivatives thereof, etc. The alkyl group of the phosphate ester-based surfactants includes styrenated phenols, nonylphenols, lauryl alcohols, tridecyl alcohols, octylphenols, etc.

[0070] Commercially available examples of phosphate ester dispersants include ADEKACOL (TS-230E, CS-141E, CS-1361E, CS-279, PS-440E, PS-810E, PS-807, PS-984: all manufactured by ADEKA Corporation, "ADEKACOL" is a registered trademark of the company), PLYSURF (A208B, A208F, A208N, A219B, DB-01, M208F: all manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "PLYSURF" is a registered trademark of the company), and Phosphanol (RS-710, RL-310, RB-410, RL-210, RS-610, RD-720N: all manufactured by Toho Chemical Industry Co., Ltd., "Phosphanol" is a registered trademark of the company). Among the above commercially available products, Adekacol TS-230E, CS-141E, and PS-440E are preferred, with Adekacol TS-230E being more preferred.

[0071] The content of the (F) phosphate ester-based dispersant is preferably 0.05 to 0.5 parts by mass relative to the total mass of the photosensitive resin composition.

[0072] In addition, the total mass (m E ) relative to the mass (m F ) ratio (m F / m E) is preferably 0.1 to 1.0, more preferably 0.2 to 0.8. The total mass (m E ) relative to the mass (m F When the proportion of ) is within the above range, it becomes possible to form a highly precise pattern while suppressing jagged edges of the pattern and residues derived from silica particles on the substrate.

[0073] The dispersion used in the photosensitive resin composition of the present invention can be prepared by mixing and dispersing the above components (A) to (F) using an appropriate method.

[0074] 7. Solvent In addition to the components (A) to (F), the photosensitive resin composition of the present invention preferably contains a solvent as component (G). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of suitable acetic acid esters include glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These can be dissolved and mixed alone or in combination of two or more to form a uniform solution composition.

[0075] Furthermore, the photosensitive resin composition of the present invention may contain additives such as resins other than component (A), such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than silica, leveling agents, antifoaming agents, surfactants, and coupling agents, as needed.

[0076] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants, etc. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

[0077] The photosensitive resin composition of the present invention preferably contains, in solids excluding the solvent (including monomers that become solids after curing), an unsaturated-group-containing photosensitive resin (Component A), a photopolymerizable monomer having at least two unsaturated bonds (Component B), a photopolymerization initiator (Component C), at least one light-shielding component selected from black pigments, mixed-color pigments, and light-shielding materials (Component D), silica particles (Component E), and a phosphate ester-based dispersant (Component F). The amount of solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass of the total amount.

[0078] The photosensitive resin composition of the present invention for black resist can be produced by mixing (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component dispersion in which a light-shielding component is dispersed in a solvent, and (E) a silica particle dispersion in which silica particles are dispersed in a solvent. The (E) silica particle dispersion contains (F) a phosphate ester-based dispersant.

[0079] By incorporating the phosphate ester-based dispersant (F) into the silica particle dispersion (E) in advance, the storage stability of the silica dispersion can be improved, and the formation of aggregates can be prevented when the silica dispersion is mixed with other resin components.

[0080] Furthermore, a 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 curing by irradiating with light (including ultraviolet light, radiation, etc.). A photomask or the like is used to provide areas that are exposed to light and areas that are not, and only the areas that are exposed to light are cured while the other areas are dissolved in an alkaline solution, thereby obtaining a desired pattern.

[0081] Furthermore, a color filter or a touch panel having the light-shielding film of the present invention as a black matrix can be produced, for example, by forming a light-shielding film having a thickness of 1.0 to 2.0 μm on a transparent substrate, and then forming red, blue, and green pixels 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.

[0082] The light-shielding film obtained by curing the photosensitive resin composition of the present invention can also be used as a black column spacer in a liquid crystal display device. For example, a single black resist can be used to form multiple sections with different film thicknesses, one of which can function as a spacer and the other as a black matrix.

[0083] Each step of the method for forming a light-shielding film by coating and drying a photosensitive resin composition will now be specifically illustrated.

[0084] The photosensitive resin composition can be applied to a substrate by any of the known methods, such as immersion in a solution, spraying, or using a roller coater, land coater, slit coater, or spinner. After applying the composition to a desired thickness using these methods, the solvent is removed (prebaked) to form a coating. Prebaking can be performed by heating in an oven or hot plate, vacuum drying, or a combination of these. The heating temperature and heating time in prebaking can be selected appropriately depending on the solvent used, but it is preferably performed at 80 to 120°C for 1 to 10 minutes.

[0085] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. The wavelength of the radiation is preferably in the range of 250 to 450 nm. Developers suitable for this alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. These developers can be selected appropriately depending on the characteristics of the resin layer, and adding a surfactant is also effective if necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developer or ultrasonic cleaner. After alkaline development, the film is usually washed with water. Examples of development methods that can be used include shower development, spray development, dip (immersion) development, and puddle (puddle) development.

[0086] After development in this manner, a heat treatment (post-baking) is carried out at 180 to 250°C for 20 to 100 minutes. This post-baking is carried out for purposes such as increasing the adhesion between the patterned cured film (light-shielding film) and the substrate. As with pre-baking, this is carried out by heating using an oven, a hot plate, or the like. The patterned cured film (light-shielding film) of the present invention is formed through various steps using a photolithography method. Then, polymerization or curing (sometimes collectively referred to as curing) is completed by heat, thereby obtaining a light-shielding film having the desired pattern. The curing temperature in this case is preferably 160 to 250°C.

[0087] As described above, the photosensitive resin composition for black resist of the present invention is not only suitable for forming a fine pattern by procedures such as exposure to light and alkali development, but also can provide a light-shielding film that is similarly excellent in light-shielding properties, adhesion, electrical insulation properties, heat resistance, and chemical resistance, even when a pattern is formed by conventional screen printing.

[0088] The photosensitive resin composition for black resist of the present invention can be suitably used as a coating material. In particular, color filter inks used in liquid crystal display devices or imaging devices, and the light-shielding films formed therefrom, are useful as color filters, black matrices for liquid crystal projection, and the like. Furthermore, the photosensitive resin composition for black resist of the present invention can be used not only as a color filter ink for color liquid crystal displays, but also as an ink material for color separation or light-shielding in various multicolor display devices, such as organic electroluminescent devices typified by organic electroluminescent devices, color liquid crystal display devices, color facsimiles, and image sensors. The color filter of the present invention can reduce reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, and, for example, reflection of light emitted from an organic electroluminescent device when used in an organic electroluminescent device. In other words, it can improve contrast in bright areas by reducing reflection of external light, and improve luminous efficiency by improving light extraction efficiency from the light-emitting side. [Example]

[0089] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0090] First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin, component (A), will be explained. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0091] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter (weight: W0(g)), weighed (W1(g)), and heated at 160°C for 2 hours, and the weight (W2(g)) was calculated from the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0092] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0093] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0094] [Average particle size] The average particle size of the silica particles was determined by the cumulant method using a particle size distribution analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) that uses dynamic light scattering.

[0095] The abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of general formula (1) in which X is a fluorene-9,9-diyl group and R1 to R4 are hydrogen atoms. DCPMA: dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: styrene AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride TEAB: Tetraethylammonium bromide AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine PGMEA: Propylene glycol monomethyl ether acetate

[0096] [Synthesis Example 1] A 500 ml four-neck flask equipped with a reflux condenser was charged with BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) and stirred at 100-105°C for 20 hours to react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged to the flask and stirred at 120-125°C for 6 hours to obtain polymerizable unsaturated group-containing alkali-soluble resin (A)-1. The solids concentration of the resulting resin solution was 56.1 mass%, the acid value (solids equivalent) was 103 mg KOH / g, and the Mw by GPC analysis was 3600.

[0097] [Synthesis Example 2] PGMEA (300 g) was placed in a 1 L four-neck flask equipped with a reflux condenser, and the flask was purged with nitrogen and then heated to 120°C. Next, a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol), and AIBN (10 g) dissolved therein was added dropwise from a dropping funnel to the flask over 2 hours, followed by stirring at 120°C for an additional 2 hours to obtain a copolymer solution.

[0098] Next, after replacing the atmosphere in the flask with air, AA (24.0 g, 0.33 moles (95% of the moles of GMA added)), TDMAMP (0.8 g), and HQ (0.15 g) were added to the resulting copolymer solution and stirred at 120 ° C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the moles of AA added) and TEA (0.5 g) were added to the resulting polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C for 4 hours to obtain unsaturated group-containing alkali-soluble resin (A)-2. The solids concentration of the resin solution was 46.0 mass%, the acid value (solids equivalent) was 76 mg KOH / g, and the Mw by GPC analysis was 5300.

[0099] Photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared in the amounts (unit: parts by mass) shown in Table 1. The ingredients used in Table 1 are as follows.

[0100] (Polymerizable unsaturated group-containing alkali-soluble resin) (A)-1: Alkali-soluble resin solution (solid content concentration: 56.1% by mass) obtained in Synthesis Example 1 above (A)-2: Alkali-soluble resin solution (solid content concentration: 46.0% by mass) obtained in Synthesis Example 2 above

[0101] (Photopolymerizable monomer) (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd., "Aronix" is a registered trademark of the company)

[0102] (Photopolymerization initiator) (C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (Irgacure OXE-02, manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company) (C)-2: ADEKA Arcles NCI-831, manufactured by ADEKA Corporation, "ADEKA Arcles" is a registered trademark of the company.

[0103] (Carbon black dispersion) (D): Carbon black concentration 25.0% by mass, polymer dispersant concentration 2.0% by mass, PGMEA dispersion (solid content 35.0% by mass) of dispersed resin (alkali-soluble resin (A-1) of Synthesis Example 1 (solid content 8.0% by mass))

[0104] (E)-1: Silica PGMEA dispersion "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration 40% by mass, average particle size 50 nm) (E)-2: Silica PGMEA dispersion "YA010C" (manufactured by Admatechs Co., Ltd., solid content concentration 20% by mass, average particle size 10 nm) (E)-3: Silica PGMEA dispersion "YC100C" (manufactured by Admatechs Co., Ltd., solid content concentration 50% by mass, average particle size 100 nm)

[0105] (dispersant) (F)-1: ADEKA COLE TS-230E (manufactured by ADEKA Corporation, "ADEKA COLE" is a registered trademark of the company) (F)-2: Adekacol PS-440E (ADEKA Corporation) (F)-3: Adekacol CS-141E (ADEKA Corporation) (F)-4: DISPERBYK 167 (manufactured by BYK Japan Co., Ltd., "DISPERBYK" is a registered trademark of BYK, solid content concentration 52% by mass) (F)-5: DISPERBYK 2000 (manufactured by BYK Japan Co., Ltd., solid content concentration 40% by mass)

[0106] (F)-1 to (F)-3 are phosphate ester dispersants, (F)-4 is a urethane dispersant, and (F)-5 is an acrylic dispersant.

[0107] (solvent) (G)-1: Propylene glycol monomethyl ether acetate (PGMEA) (G)-2: Cyclohexanone (ANON)

[0108] [Table 1]

[0109] [evaluation] A cured film (light-shielding film) for use in evaluation was prepared by curing the photosensitive resin composition for black resist as follows.

[0110] (Preparation of hardened film (light-shielding film) for evaluation of development characteristics) The photosensitive resin composition shown in Table 1 was previously exposed to a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm. 2 The coating was applied using a spin coater to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 u.s., so that the film thickness after heat curing would be 1.2 μm, and the substrate was prebaked at 90°C for 1 minute on a hot plate to produce a hardened film (light-shielding film). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with a line / space of 10 μm / 50 μm was placed on the dried light-shielding film, and the i-line illuminance was 30 mW / cm. 2 50mJ / cm with an ultra-high pressure mercury lamp 2 The exposed portion was exposed to ultraviolet light to cause a photo-curing reaction.

[0111] Next, the exposed cured film (light-shielding film) was immersed in a 0.04% potassium hydroxide solution at 25°C at 1 kgf / cm 2 After developing for +10 seconds and +20 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2The unexposed portions of the cured film (light-shielding film) were removed to form a cured film pattern on the glass substrate, which was then 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 9 and Comparative Examples 1 to 4.

[0112] The cured films (light-shielding films) obtained by curing the photosensitive resin compositions for black resists of Examples 1 to 9 and Comparative Examples 1 to 4 obtained above were evaluated for the following items.

[0113] [Development characteristics evaluation] (pattern linearity) (Evaluation method) The post-baked 10 μm mask pattern was observed using an optical microscope and a scanning electron microscope (SEM) to check for jagged edges on the pattern and residues from silica particles on the substrate. The pattern linearity was evaluated for both BT+10 seconds and BT+20 seconds. A score of ○ or higher was considered a pass.

[0114] (Evaluation criteria for development characteristics) ○: No jagged edges are observed on the pattern edges △: Jagged edges are observed in some areas of the pattern. ×: Jagged edges of the pattern are observed throughout the entire pattern.

[0115] (Residue evaluation criteria) ○: No residues originating from silica particles were observed at the pattern edges and openings △: Residues from silica particles are found in some areas of the pattern edges and openings. ×: Residues derived from silica particles are observed throughout the pattern edge and opening.

[0116] [Optical density evaluation] (Evaluation method) The optical density (OD) of the prepared cured film (light-shielding film) was evaluated using a Macbeth transmission densitometer. The thickness of the cured film (light-shielding film) formed on the substrate was measured, and the optical density (OD) value was divided by the film thickness to obtain OD / μm.

[0117] The optical density (OD) was calculated using the following formula (1). Optical density (OD)=-log 10 T(1) (T indicates transmittance)

[0118] [Reflectance evaluation] (Evaluation method) For a substrate with a cured film (light-shielding film) prepared in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, the reflectance of each of the cured film (light-shielding film) side and the substrate (glass substrate) side was measured at an incident angle of 2° using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0119] The evaluation results are shown in Table 2.

[0120] [Table 2]

[0121] It was confirmed that the photosensitive resin compositions for black resists of Examples 1 to 9 were able to reduce the reflectance from the substrate side compared to a system that did not contain silica particles (Comparative Example 1). Furthermore, the evaluation results of Examples 1 to 9 confirmed that the photosensitive resin compositions for black resists containing the alkali-soluble resin solution (A-1) and a phosphate ester-based dispersant had better development characteristics (pattern linearity). Furthermore, the evaluation results of Examples 1 to 9 confirmed that the photosensitive resin compositions for black resists containing the alkali-soluble resin solution (A-1) and a phosphate ester-based dispersant had better pattern linearity and residue on the substrate compared to Comparative Examples 1 and 2, which did not contain any dispersant, and Comparative Examples 3 and 4, which used a urethane-based dispersant and an acrylic-based dispersant. [Industrial Applicability]

[0122] The photosensitive resin composition of the present invention can provide a photosensitive resin composition for black matrices that achieves both high light-shielding properties and low reflectance, and a light-shielding film, a color filter, and a touch panel using the same. Furthermore, the color filter and the touch panel can provide various display devices with excellent visibility.

Claims

1. (A) an unsaturated group-containing photosensitive resin; (B) a photopolymerizable monomer having at least two unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials; (E) silica particles; (F) a phosphate ester-based dispersant (however, the (F) phosphate ester-based dispersant excludes a (meth)acrylate phosphate compound); A photosensitive resin composition for black resist, comprising: the content of the light-shielding component (D) is 20 to 80 mass % based on the solid content in the photosensitive resin composition for black resist, The (F) phosphate ester-based dispersant includes a phosphate monoester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, a phosphate diester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, or a phosphate triester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, Photosensitive resin composition for black resist.

2. 2. The photosensitive resin composition for black resist according to claim 1, wherein the unsaturated group-containing photosensitive resin (A) is an unsaturated group-containing photosensitive resin obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol represented by general formula (1) with (meth)acrylic acid, with a polybasic carboxylic acid or an anhydride thereof. 【Chemistry 1】 (In formula (1), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is —CO—, —SO ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ -, -CH ２ -, -C(CH ３ ) ２ -, -O-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer of 0 to 10. 【Chemistry 2】

3. The total mass (m Ｅ ) the mass (m Ｆ ) ratio (m Ｆ / m Ｅ 3. The photosensitive resin composition for black resist according to claim 1, wherein the value of (a) is 0.1 to 1.

0.

4. 4. The photosensitive resin composition for black resist according to claim 1, wherein the average particle size of the silica particles (E) is 1 to 100 nm.

5. The total mass (m Ｄ ) the mass (m Ｅ ) ratio (m Ｅ / m Ｄ 5. The photosensitive resin composition for black resist according to claim 1, wherein the ratio of the total mass of the black resist to the total mass of the non-black resist is 0.01 to 0.

20.

6. A method for producing a photosensitive resin composition for black resist, which comprises mixing (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) a light-shielding component dispersion in which at least one light-shielding component selected from the group consisting of a black pigment, a mixed color pigment, and a light-shielding material is dispersed in a solvent, and (E) a silica particle dispersion in which silica particles are dispersed in a solvent, In the mixing step, the light-shielding component dispersion is mixed in an amount such that the amount of the light-shielding component (D) relative to the solid content in the photosensitive resin composition for black resist is 20 to 80 mass %; the (E) silica particle dispersion contains (F) a phosphate ester-based dispersant (provided that the (F) phosphate ester-based dispersant excludes a (meth)acrylate phosphate compound); The (F) phosphate ester-based dispersant comprises a phosphoric acid monoester of a polyoxyethylene alkyl ether or a polyoxyethylene alkylaryl ether, a phosphoric acid diester of a polyoxyethylene alkyl ether or a polyoxyethylene alkylaryl ether, or a phosphoric acid triester of a polyoxyethylene alkyl ether or a polyoxyethylene alkylaryl ether.

7. A light-shielding film obtained by curing the photosensitive resin composition for black resist according to any one of claims 1 to 5.

8. A color filter having the light-shielding film according to claim 7 as a black matrix.

9. A touch panel having the light-shielding film according to claim 7 as a black matrix.

10. A display device comprising the color filter according to claim 8 or the touch panel according to claim 9.

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