Photosensitive resin composition for black resist, method for producing the same, light-shielding film, color filter, touch panel, and display device

Abstract

To provide a photosensitive resin composition for black resist, which has a high light shielding property and low reflectivity, can form a high precision pattern, and can suppress occurrence of aggregated foreign matter.SOLUTION: A photosensitive resin composition for black resist comprises: an unsaturated group-containing photosensitive resin (A); a photopolymerizable compound having at least 2 or more unsaturated groups (B); a photoinitiator (C); at least one light shielding component selected from the group consisting of a black pigment, a mixed color pigment, and a light shielding material (D); silica particles (E); and a dispersant (F). The dispersant (F) has an acid value and an amine value, and both of the acid value and the amine value are 10 mgKOH / g to 80 mgKOH / g. A ratio of a total mass (mE) of the silica particles (E) to a total mass (mF) of the dispersant (F), (mF / mE), is 0.02 to 0.60.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

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

[0004] For this reason, there is a demand for a photosensitive resin composition for a black resist that can obtain a light-shielding film having both high light-shielding properties and low reflectivity.

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

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, as a result of investigations by the present inventors, in the black photosensitive resin composition described in Patent Document 1, in pattern formation, there were problems such as jaggedness occurring at the pattern edge portion and the generation of aggregated foreign matter derived from silica particles on the black matrix.

[0008] The present invention has been made in view of such points, and provides a photosensitive resin composition for a black resist having high light-shielding properties and low reflectance, capable of forming a high-definition pattern, and suppressing the generation of aggregated foreign matter, 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 or the touch panel.

Means for Solving the Problems

[0009] The photosensitive resin composition for black resist according to the present invention comprises: (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable compound having at least two or more 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, and (F) a dispersant, wherein the (F) dispersant has an acid value and an amine value, both the acid value and the amine value are 10 mgKOH / g or more and 80 mgKOH / g or less, and the ratio (m E / m F ) of the total mass (m F ) of the (F) dispersant to the total mass (m E ) of the (E) silica particles is 0.02 to 0.60.

[0010] The method for producing a photosensitive resin composition for black resist according to the present invention comprises mixing (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable compound having at least two or more 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 black pigments, mixed-color pigments, and light-shielding materials 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 dispersant, the (F) dispersant has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH / g or more and 80 mgKOH / g or less. When mixing, the ratio (m E / m F ) of the total mass (m F ) of the (F) dispersant to the total mass (m E ) of the (E) silica particles in the photosensitive resin composition for black resist is 0.02 to 0.60.

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

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

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

[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, there can be provided a photosensitive resin composition for black resist having high light-shielding properties and low reflectance, enabling formation of a high-definition pattern, and suppressing generation of aggregated foreign matter, a light-shielding film formed by curing the composition, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or the touch panel.

Embodiments for Carrying Out the Invention

[0016] Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resist of the present invention (hereinafter abbreviated as "photosensitive resin composition") contains (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable compound having at least two or more 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 dispersant. Hereinafter, the components (A) to (F) will be described.

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

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

[0019] The unsaturated group-containing photosensitive resin as the component (A) is preferably a bisphenol type epoxy compound represented by the following general formula (1).

[0020] [Chemical formula]

[0021] (In formula (1), R1, R2, R3 and R4 are each independently either 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 the general formula (2) or a single bond, and l is an integer of 0 to 10.)

[0022] [Chemical formula]

[0023] The bisphenol type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. In this reaction, since oligomerization of the diglycidyl ether compound generally occurs, it contains an epoxy compound containing two or more bisphenol skeletons.

[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-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like.Among these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0025] Examples of the (a) dicarboxylic acid or tricarboxylic acid monoanhydride that reacts with the hydroxy group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include chain hydrocarbon dicarboxylic acid or tricarboxylic acid monoanhydrides, alicyclic dicarboxylic acid or tricarboxylic acid monoanhydrides, aromatic dicarboxylic acid or tricarboxylic acid monoanhydrides, and the like. Here, examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid monoanhydride include monoanhydrides of 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, and the like. Furthermore, it includes monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced, and the like. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid monoanhydride include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like. Furthermore, it also includes monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced, and the like. Examples of the aromatic dicarboxylic acid or tricarboxylic acid monoanhydride include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like. Furthermore, it includes dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced and their monoanhydrides.

[0026] In addition, as the acid dianhydride of (b) tetracarboxylic acid to be reacted with epoxy (meth)acrylate, an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, or an aromatic tetracarboxylic acid is used. Here, examples of the acid dianhydride of a chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced. Examples of the acid dianhydride of an alicyclic tetracarboxylic acid include acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced. Examples of the acid dianhydride of an aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenyl ether tetracarboxylic acid. Furthermore, it includes acid dianhydrides of tetracarboxylic acids into which any substituent has been introduced.

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

[0028] In addition, the reaction between the epoxy compound and (meth)acrylic acid, and the reaction between the epoxy (meth)acrylate obtained from this reaction and the polybasic carboxylic acid or its acid anhydride are not particularly limited, and known methods can be adopted. Further, for the unsaturated group-containing photosensitive resin synthesized by the above reaction, its weight average molecular weight (Mw) is preferably from 2000 to 10000, and the acid value is preferably from 30 to 200 mgKOH / g. The above acid value can be determined by dissolving the resin solution in dioxane and titrating it with a 1 / 10N - KOH aqueous solution using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). Further, the weight average molecular weight (Mw) of the above unsaturated group-containing photosensitive resin can be measured using, for example, gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation).

[0029] Another example of a resin preferred as the unsaturated group-containing photosensitive resin as the component (A) includes a copolymer of (meth)acrylic acid, (meth)acrylic acid ester, etc., and a resin having a (meth)acryloyl group and a carboxyl group. Examples of the above resin include a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting (meth)acrylic acid, and finally reacting with an anhydride of a dicarboxylic acid or a tricarboxylic acid, and containing a polymerizable unsaturated group-containing alkali-soluble resin. The above copolymer is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid as shown in JP-A-2014-111722, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g, and a polymerizable unsaturated group-containing alkali-soluble resin which is a polymer having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mg / KOH, containing 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 shown in JP-A-2018-141968 can be referred to.

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

[0031] 2. (B) Component Examples of the photopolymerizable compound having at least two or more unsaturated bonds, which is the (B) component 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylic acid esters. Also included are dendritic polymers having a (meth)acrylic group as a compound having an ethylenic double bond. Only one type of these photopolymerizable compounds may be used alone, or two or more types may be used in combination. Further, the photopolymerizable compound having at least two ethylenic unsaturated bonds can play a role of crosslinking the molecules of the contained alkali-soluble resin. In order to exhibit this function, it is preferable to use one having three or more unsaturated bonds. Also, it is preferable that the acrylic equivalent obtained by dividing the molecular weight of the photopolymerizable compound by the number of (meth)acrylic groups in one molecule is 50 to 300, and more preferably 80 to 200. Note that the (B) component does not have a free carboxy group.

[0032] Examples of the compound having an unsaturated bond that can be included in the composition as the component (B) and having a (meth)acryloyl group include dendritic polymers obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, dendritic polymers obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (3) with a polyvalent mercapto compound represented by the following general formula (4) are included.

[0033]

Chemical formula

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

[0035]

Chemical formula

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

[0037] Examples of the polyfunctional (meth)acrylate represented by the general formula (3) include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate. These compounds may be used alone, or two or more of them may be used in combination.

[0038] Examples of the polyvalent mercapto compound represented by the 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), and the like. These compounds may be used alone, or two or more of them may be used in combination.

[0039] The mixing ratio of component (A) and component (B) is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20 in terms of weight ratio (A) / (B). When the mixing ratio of component (A) is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and in the unexposed part, the acid value of the coating film is less likely to decrease, so that the decrease in solubility in the alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges or lack of sharpness are less likely to occur. Also, when the mixing ratio of component (A) is 90 / 10 or less, the ratio of the photoreactive functional groups in the resin is sufficient, so that the formation of the desired crosslinked structure can be carried out. Also, since the acid value in the resin component is not too high, the solubility in the alkaline developer in the exposed part is less likely to increase, so that the formed pattern can be prevented from becoming thinner than the target line width and pattern dropout can be suppressed.

[0040] 3. Component (C) Examples of the photoinitiator, which is the component (C) according to this embodiment, include acetophenones such as acetophenone, 2,2 - diethoxyacetophenone, p - dimethylacetophenone, p - dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p - tert - butylacetophenone; benzophenones such as benzophenone, 2 - chlorobenzophenone, p,p’ - bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; imidazole - based compounds such as 2 - (o - chlorophenyl) - 4,5 - 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; halomethylthiazole compounds such as 2 - trichloromethyl - 5 - styryl - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - cyanostyryl) - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - methoxystyryl) - 1,3,4 - oxadiazole; halomethyl - S - triazine - based compounds such as 2,4,6 - tris(trichloromethyl) - 1,3,5 - triazine, 2 - methyl - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - phenyl - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - chlorophenyl) - 4,6 - bis(trichloromethyl - 1,3,5 - triazine, 2 - (4 - methoxyphenyl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methoxynaphthyl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methoxystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (3,4,5 - trimethoxystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine, 2 - (4 - methylthioystyryl) - 4,6 - bis(trichloromethyl) - 1,3,5 - triazine;O-acyl oxime-based 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-acetyl oxime; sulfur compounds such as benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine are included. These photoinitiators may be used alone, or two or more of them may be used in combination.;

[0041] Examples of the group of O-acyl oxime-based compounds that can be preferably used include O-acyl oxime-based photoinitiators represented by the following general formula (5) and the following general formula (6). Even among these compound groups, when a light-shielding component is used at a high concentration, it is preferable to use an O-acyl oxime-based photoinitiator having a molar extinction coefficient of 10,000 or more at 365 nm. In the present invention, the "photoinitiator" is used in a meaning including a sensitizer.;

[0042]

Chemical formula

[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, and R 11 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be a linear, branched, or cyclic alkyl group.)

[0044] [Chemical Formula]

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

[0046] The amount of the photoinitiator as component (C) is preferably 3 parts by weight or more and 30 parts by weight or less, more preferably 5 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight in total of the components (A) and (B). When the blending ratio of component (C) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be achieved. When the blending ratio of component (C) is 30 parts by weight or less, an appropriate sensitivity can be obtained, so that a desired pattern line width and a desired pattern edge can be obtained.

[0047] 4. Component (D) As the light-shielding components such as black pigments, mixed-color organic pigments, and light-shielding materials which are component (D) according to this embodiment, as long as they are dispersed with an average particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter), known light-shielding components can be used without particular limitation.

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

[0049] Examples of the mixed-color organic pigment as component (D) include pigments in which at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed.

[0050] The above component (D) may be used alone as only one type thereof, or two or more types may be used in combination, depending on the function of the target photosensitive resin composition.

[0051] In addition, examples of the organic pigments that can be used when using a mixed-color organic pigment as component (D) include those with the following numbers by Color Index name, but are not limited thereto. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0052] (D) Regarding the blending ratio of the light-shielding component of the component, it can be arbitrarily determined according to the desired light-shielding degree, but it is preferably 20% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 70% by mass or less, based on the total mass of the solid content in the photosensitive resin composition. When using an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black as the light-shielding component of component (D), it is particularly preferably 40% by mass or more and 60% by mass or less based on the solid content in the photosensitive resin composition. When the light-shielding component is 20% by mass or more based on the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light-shielding component is 80% by mass or less based on the solid content in the photosensitive resin composition, the content of the photosensitive resin that becomes the original binder does not decrease, so the desired development characteristics and film-forming ability can be obtained.

[0053] The above-mentioned component (D) is usually mixed with other compounding components as a light-shielding component dispersion dispersed in a solvent, and a dispersant can be added at that time. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (such as compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation.

[0054] Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). In particular, the above-mentioned dispersant preferably has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the colorant, and is a cationic polymer dispersant having an amine value in the range of 1 to 100 mgKOH / g and a number average molecular weight (Mn) in the range of 1000 to 100000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the light-shielding component. Note that high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but those without dispersion promoting ability are not treated as dispersants. However, it is not limited to being used for the purpose of stabilizing dispersion.

[0055] Also, the ratio (m D / m E ) of the total mass (m E ) of the (E) silica particles (described later) to the total mass (m D ) of the above-mentioned (D) light-shielding component is preferably 0.01 to 0.20, more preferably 0.05 to 0.10. When the ratio of the total mass (m D ) of the (E) silica particles to the total mass (m E ) of the (D) light-shielding component is within the above range, it is possible to achieve both high light-shielding property and low reflectance.

[0056] 5. Component (E) The silica particles as component (E) are not particularly limited in terms of production methods such as gas-phase reaction or liquid-phase reaction, and shape (spherical, non-spherical).

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

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

[0059] In addition, since the reflection caused by the difference in refractive index between the transparent substrate and the light-shielding film formed thereon can be suppressed, the reflection can be suppressed without separately providing an antireflection film or the like on the substrate.

[0060] The average particle diameter of the above silica particles is preferably 1 to 100 nm, and more preferably 10 to 90 nm. Compared with the case of small particle diameters such as several nm, it is considered that aggregation of silica particles is less likely to occur at sizes within the above range. Thereby, within the range of the above particle diameter, since the silica particles are excellent in dispersion stability, they can be uniformly present in the light-shielding film. Therefore, variations in the reflectance on the light-shielding film are less likely to occur.

[0061] In addition, the content of the above silica particles is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to the total mass of the photosensitive resin composition containing a solvent. When the content of the silica particles is within the above range, it is possible to achieve a reduction in reflectance while ensuring good light patterning properties.

[0062] The average particle diameter of the above silica particles can be measured by the cumulant method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) for dynamic light scattering.

[0063] In addition, silica particles with a refractive index of 1.10 to 1.47 can be used. Silica particles with a refractive index of 1.45 to 1.47, which are ordinary silica particles, can be used. By using hollow silica particles having a low refractive index, the refractive index of the light-shielding film can be made lower than that of a light-shielding film containing only ordinary silica particles.

[0064] In addition, the refractive index of the silica particles can be determined from a transparent mixed solution obtained by mixing the above silica particles processed into a powder form with a standard refractive index liquid having a known refractive index. The refractive index of the above silica particles can be measured using an Abbe refractometer.

[0065] The shape of the above silica particles may be a spherical shape or an elliptical shape. The shape of the silica particles used in the present invention is preferably a spherical shape.

[0066] The above silica particles preferably have a sphericity of 1.0 to 1.5. If the sphericity of the silica particles is within this range, the particle shape becomes close to a sphere. Therefore, it can be uniformly filled in a light-shielding film with a thin film thickness, and a light-shielding film can be formed in which the above silica particles are not exposed to the outside from the film surface while maintaining the surface smoothness of the film. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained.

[0067] The sphericity of the above silica particles can be determined from the ratio of the longest diameter to the shortest diameter of the particles (average value of any 100 silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values obtained by photographing the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter from the obtained micrograph.

[0068] The silica particles as the above-mentioned (E) component can be mixed with other compounding components as a silica particle dispersion dispersed in a solvent. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. In this embodiment, the above-mentioned silica particle dispersion contains a (F) dispersant described later.

[0069] 6. (F) Component The dispersant as the (F) component according to this embodiment has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH / g or more and 80 mgKOH / g or less. When the amine value of the dispersant is 10 mgKOH / g or more, the dispersibility of the silica particles can be enhanced. On the other hand, a dispersant having only an amine value, although it enhances the dispersibility of the silica particles, reduces the solubility of the silica particles in the developer, so that it remains as a residue at the pattern edge portion, reducing the linearity. In contrast, when the amine value of the dispersant is 10 mgKOH / g or more and the acid value is also 10 mgKOH / g or more, it is possible to form a high-definition pattern while enhancing the dispersibility of the silica particles. On the other hand, by setting both the acid value and the amine value to 80 mgKOH / g or less, the solubility of the silica particles protected by the dispersant in the developer does not increase excessively, and it is possible to suppress a decrease in the fineness of the formed pattern. From the above viewpoints, it is preferable that either the amine value or the acid value of the dispersant is 30 mgKOH / g or more and 80 mgKOH / g or less, and it is more preferable that both are 30 mgKOH / g or more and 80 mgKOH / g or less.

[0070] The acid value of the dispersant as the (F) component means the number of mg of KOH required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with JIS-K0070. The amine value of the dispersant as the (F) component means the number of mg of KOH equivalent to the amount of acid (such as acetic acid) required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with JIS-K7237.

[0071] Examples of the dispersant as the above (F) component include alkylammonium salts and alkylolammonium salts of acidic polymers, or alkylammonium salts and alkylolammonium salts of polymer copolymers having acid groups, neutral salts of polymers having alkylamino groups, phosphate ester salts of polymer copolymers, and the like. Among these, alkylammonium salts of acidic polymers or alkylammonium salts of polymer copolymers having acid groups are preferred. By using an alkylammonium salt or alkylolammonium salt of an acidic polymer, or an alkylammonium salt or alkylolammonium salt of a polymer copolymer having an acid group as the dispersant, the generation of aggregated foreign matters derived from silica particles can be more significantly suppressed.

[0072] Examples of commercially available products of the dispersant as the (F) component include DISPERBYK-140, 142, 145, 2001, 2025, 9076 (all manufactured by BYK Japan Co., Ltd., "DISPERBYK" is the company's registration), and the like. Among the above commercially available products, DISPERBYK-140, 142, 9076 are preferred, and DISPERBYK-140, 9076 are more preferred.

[0073] The content of the (F) dispersant is preferably 0.01 to 0.5 parts by mass based on the total mass of the photosensitive resin composition containing the solvent.

[0074] Also, the ratio (m E ) of the total mass (m F ) of the above (F) dispersant to the total mass (m F ) of the above (E) silica particles (m E / m E ) is preferably 0.02 to 0.6, and more preferably 0.03 to 0.4. When the ratio of the total mass (m F ) of the above (F) dispersant to the total mass (m E ) of the silica particles is within the above range, while reducing the reflectance on the glass substrate side, the dispersibility of the silica particles can be improved, and the generation of aggregated foreign matters derived from the silica particles can be suppressed.

[0075] By mixing and dispersing the above components (A) to (F) in an appropriate manner, a dispersion used in the photosensitive resin composition of the present invention can be prepared.

[0076] 7. Solvent In the photosensitive resin composition of the present invention, in addition to the components (A) to (F), it is preferable to use a solvent as the 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; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, 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. By dissolving and mixing these alone or in combination of two or more, a uniform solution-like composition can be obtained.

[0077] Further, in the photosensitive resin composition of the present invention, resins other than the component (A) such as epoxy resin, curing agents, curing accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, fillers other than silica, leveling agents, defoaming agents, surfactants, coupling agents, and other additives can be blended as necessary.

[0078] Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, mica, alumina, and the like. Examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0079] The photosensitive resin composition of the present invention preferably contains, in the solid content excluding the solvent (the solid content includes monomers that become solid components after photocuring), an unsaturated group-containing photosensitive resin as component (A), a photopolymerizable compound having at least two or more unsaturated bonds as component (B), a photoinitiator as component (C), at least one light-shielding component selected from a black pigment, a mixed-color pigment, and a light-shielding material as component (D), silica particles as component (E), and a dispersant as component (F). The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass based on the total amount.

[0080] The photosensitive resin composition of the present invention can be used to produce a photosensitive resin composition for black resist by mixing (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable compound, (C) a photoinitiator, (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 above (E) silica particle dispersion contains the above (F) dispersant.

[0081] By previously incorporating the (F) dispersant into the (E) silica particle dispersion, the dispersion stability of the silica dispersion can be improved, and the generation of aggregated foreign matters can be prevented when mixing with other resin components.

[0082] In addition, the light-shielding film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent, and irradiating with light (including ultraviolet rays, radiation, etc.) to cure it. By using a photomask or the like to provide a portion irradiated with light and a portion not irradiated with light, only the portion irradiated with light is cured, and the other portion is dissolved in an alkaline solution, whereby a desired pattern can be obtained.

[0083] In addition, 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 film thickness of 1.0 to 2.0 μm on a transparent substrate, and forming each red, blue, and green pixel by photolithography after forming the light-shielding film, and also by injecting red, blue, and green inks into the light-shielding film by an inkjet process.

[0084] The light-shielding film obtained by curing the photosensitive resin composition of the present invention can also be used as a black column spacer of a liquid crystal display device. For example, using a single black resist, a plurality of portions having different film thicknesses can be produced, and one can function as a spacer and the other can function as a black matrix.

[0085] Each step of the method for forming a light-shielding film by coating and drying the photosensitive resin composition will be specifically exemplified.

[0086] As a method for applying the photosensitive resin composition to a substrate, any method such as a known solution immersion method, spray method, roller coater machine, land coater machine, slit coater machine, or spinner machine can be adopted. After coating to a desired thickness by these methods, the solvent is removed (pre-baked) to form a film. The pre-baking is performed by heating with an oven, hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking can be appropriately selected according to the solvent used, but for example, it is preferably performed at 80 to 120 °C for 1 to 10 minutes.

[0087] As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc. can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. Further, as the developer suitable for this alkali development, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant as necessary. The development temperature is preferably 20 to 35°C, and a fine image can be precisely formed using a commercially available developing machine, ultrasonic cleaner, etc. After alkali development, it is usually washed with water. As the development treatment method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid pool) development method, etc. can be applied.

[0088] After development in this way, heat treatment (post-bake) is performed at 180 to 250°C for 20 to 100 minutes. This post-bake is performed for purposes such as enhancing the adhesion between the patterned light-shielding film and the substrate. This is carried out by heating with an oven, hot plate, etc., similar to pre-bake. The patterned light-shielding film of the present invention is formed through each step by a photolithography method. Then, polymerization or curing (sometimes both are combined and called curing) is completed by heat, and a light-shielding film having a desired pattern can be obtained.

[0089] As described above, the photosensitive resin composition for black resist of the present invention is not only suitable for forming a fine pattern by operations such as exposure and alkali development, but also a light-shielding film excellent in the same light-shielding property, adhesion, electrical insulation, heat resistance, and chemical resistance can be obtained even when a pattern is formed by conventional screen printing.

[0090] The photosensitive resin composition for black resist of the present invention can be suitably used as a coating material. In particular, the ink for color filters used in liquid crystal display devices or imaging elements, and the light-shielding film formed thereby are useful as color filters, black matrices for liquid crystal projection, etc. Further, the photosensitive resin composition for black resist of the present invention can be used not only as the color filter ink of color liquid crystal displays, but also as ink materials for color separation or light shielding in various multicolor displays such as organic electroluminescent devices typified by organic EL elements, color liquid crystal display devices, color facsimiles, image sensors, etc. According to the color filter of the present invention, it is possible to reduce the reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, and for example, the reflection of light emitted from the element when used in an organic EL element. That is, it is possible to improve the bright contrast by reducing the reflection of external light and improve the luminous efficiency by improving the light extraction efficiency from the light-emitting side.

Examples

[0091] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. In the present invention, when the content of each component has 0 in the first decimal place, the notation after the decimal point may be omitted.

[0092] First, a synthesis example of the unsaturated group-containing alkali-soluble resin as the component (A) will be described. The evaluation of the resins in these synthesis examples was carried out as follows unless otherwise specified.

[0093] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)], and was determined from the following formula based on the weight [W2 (g)] after heating at 160 ° C. for 2 hours. Solid content concentration (wt%) = 100×(W2 - W0) / (W1 - W0)

[0094] [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 obtain the result.

[0095] [Molecular weight] The weight - average molecular weight (Mw) was determined by gel permeation chromatography (GPC) “HLC - 8220GPC” (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgel SuperH - 2000 (2 pieces)+TSKgel SuperH - 3000 (1 piece)+TSKgel SuperH - 4000 (1 piece)+TSKgel SuperH - 5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 °C, flow rate: 0.6 ml / min) and expressed as a value in terms of standard polystyrene (manufactured by Tosoh Corporation, PS - oligomer kit).

[0096] [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.) based on the dynamic light scattering method.

[0097] The abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: Bisphenol fluorene - type epoxy compound (reaction product of 9,9 - bis(4 - hydroxyphenyl)fluorene and chloromethyloxirane. In the compound of general formula (1), the compound where X is a fluorene - 9,9 - diyl group and R1 - R4 are hydrogen). AA: Acrylic acid BPDA: 3,3’,4,4’ - Biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0098] [Synthesis example] Into a 500 ml four-necked flask equipped with a reflux condenser, BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged and reacted with stirring at 100 to 105 °C for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask and stirred at 120 to 125 °C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A). The solid content concentration of the obtained resin solution was 56.0% by mass, the acid value (in terms of solid content) was 103 mgKOH / g, and Mw by GPC analysis was 3600.

[0099] The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared with the compounding amounts (unit: mass%) shown in Table 1. The compounding components used in Table 1 are as follows.

[0100] (Unsaturated group-containing alkali-soluble resin) (A): Unsaturated group-containing alkali-soluble resin solution (solid content concentration 56.0% by mass) obtained in the above synthesis example

[0101] (Photopolymerizable compound) (B): 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-(O-acyloxime) (Irgacure OXE-02, manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company) (C)-2: Adeka Arculex NCI-831, manufactured by Adeka Corporation, "Adeka Arculex" is a registered trademark of the company)

[0103] (Carbon black dispersion) (D): Carbon black concentration 25.0 mass%, polymer dispersant concentration 2.0 mass%, PGMEA dispersion of a dispersion resin (alkali-soluble resin (A) in the synthesis example (solid content 8.0 mass%)) (solid content 35.0 mass%)

[0104] (E): PGMEA dispersion of silica particles "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration 30 mass%, average particle diameter 50 nm)

[0105] (dispersant) (F)-1: DISPERBYK-140 (solid content concentration 52 mass%) (F)-2: DISPERBYK-142 (solid content concentration 60 mass%) (F)-3: DISPERBYK-9076 (solid content concentration 100 mass%) (F)-4: DISPERBYK-167 (solid content concentration 52 mass%) (F)-5: DISPERBYK-170 (solid content concentration 30 mass%) (F)-6: DISPERBYK-180 (solid content concentration 100 mass%) (F)-7: DISPERBYK-9077 (solid content concentration 100 mass%) Note that (F)-1 to (F)-7 are all manufactured by BYK Japan Co., Ltd., and "DISPERBYK" is the registered trademark of the company.

[0106] Also, (F)-1 is a dispersant having an alkylammonium salt structure of an acidic polymer, (F)-2 is a phosphate ester salt type dispersant of a polymer copolymer, (F)-3 is a dispersant having an alkylammonium salt structure of a polymer copolymer having an acid group, (F)-4 is a urethane-based dispersant, (F)-5 is a polymer dispersant having an acidic functional group, (F)-6 is an alkylolammonium salt type dispersant of a copolymer containing an acid group, and (F)-7 is a polymer copolymer having an amine value.

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

[0108]

Table 1

[0109] [Evaluation] A light-shielding film obtained by curing a photosensitive resin composition for a black resist for evaluation was prepared as follows.

[0110] (Preparation of Light-Shielding Film for Evaluation) The photosensitive resin composition shown in Table 1 was irradiated with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm 2 in advance with a low-pressure mercury lamp to clean the surface, and then applied onto a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Inc.) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing treatment would be 1.2 μm, and pre-baked at 90°C for 1 minute using a hot plate to prepare a light-shielding film. Next, the exposure gap was adjusted to 100 μm, a negative photomask with a line / space = 10 μm / 50 μm was placed on the dried light-shielding film, and ultraviolet rays with an i-line illuminance of 30 mW / cm 2 were irradiated with an ultra-high pressure mercury lamp at 50 mJ / cm 2 to carry out a photocuring reaction of the photosensitive portion.

[0111] Next, the exposed light-shielding film was developed at a shower pressure of 1 kgf / cm 2 using a 0.04% potassium hydroxide solution at 25°C for a development time starting from the development time (break time = BT) when the pattern began to appear, +10 seconds and +20 seconds, and then spray water washed at 5 kgf / cm 2 to remove the unexposed portion of the light-shielding film and form a light-shielding film pattern on the glass substrate, and then post-cured (post-baked) at 230°C for 30 minutes using a hot air dryer to obtain light-shielding films for evaluation according to Examples 1 to 10 and Comparative Examples 1 to 7.

[0112] The prepared light-shielding films for evaluation were evaluated for the following items.

[0113] [Pattern linearity evaluation] (Evaluation method) After this hardening (post-bake), the 10-μm mask pattern was observed for the jaggedness at the pattern edge using an optical microscope and a scanning electron microscope (SEM). Note that the pattern linearity evaluation was performed for the cases of BT + 10 seconds and BT + 20 seconds. Note that ○ or above was considered a pass.

[0114] (Evaluation criteria) ○: No jaggedness is observed at the pattern edge part △: Jaggedness is partially observed at the pattern edge part ×: Jaggedness is observed throughout the pattern edge part

[0115] [Optical density evaluation] (Evaluation method) Using a Macbeth transmission densitometer, the optical density (OD) of the prepared light-shielding film for evaluation was obtained. Also, the film thickness of the light-shielding film formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was defined as OD / μm.

[0116] The optical density (OD) was calculated by the following formula (1). Optical density (OD)= -log 10 T (1) (T indicates the transmittance)

[0117] [Reflectance evaluation] (Evaluation method) For the substrate with a light-shielding film prepared in the same manner as the above light-shielding film for evaluation, the reflectance on the substrate (glass substrate) side at an incident angle of 2° was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Technologies Corporation). Note that △ or above was considered a pass.

[0118] (Evaluation criteria) ○: The reflectance on the substrate side of the substrate with a light-shielding film is 5% or less △: The reflectance on the substrate side of the substrate with a light-shielding film is more than 5% and less than 6% ×: The reflectance on the substrate side of the substrate with a light-shielding film is 6% or more.

[0119] [Agglomerated foreign matter evaluation] (Evaluation method) The light-shielding film for evaluation after this hardening (post-bake) was observed using an optical microscope to confirm the presence or absence of agglomerated foreign matter. Note that a result of △ or higher was considered to be a pass.

[0120] (Evaluation criteria) ○: No agglomerated foreign matter was confirmed in the light-shielding film △: Agglomerated foreign matter was confirmed in a part of the light-shielding film ×: Agglomerated foreign matter was confirmed over the entire surface of the light-shielding film

[0121] The above evaluation results are shown in Table 2.

[0122] [Table 2]

[0123] As shown in Examples 1 to 10, it was found that by using a dispersant having both an acid value and an amine value of 10 mgKOH / g or more and 80 mgKOH / g or less, high-precision pattern formation can be achieved. On the other hand, when both the acid value and the amine value are greater than 80 mgKOH / g, it was found that the solubility in the developer becomes too high, resulting in deterioration of the pattern linearity.

[0124] Also, as shown in Examples 1 to 10, it was found that the jaggedness at the pattern edge portion was eliminated as compared with Comparative Examples 2 and 5 to which a dispersant having only an amine value was applied. This is presumably because although the solubility in the developer tends to decrease by adsorbing a dispersant to silica particles, the solubility of the silica particles in the developer was ensured by applying a dispersant having both an acid value and an amine value.

[0125] Also, as shown in Examples 1 to 10, it was found that by using a dispersant having an acid value and an amine value both in the range of 10 mgKOH / g or more and 80 mgKOH / g or less, the dispersion stability of silica particles can be improved and the generation of aggregated foreign matters can be suppressed. In particular, in Examples 1, 3 to 10 using a polymer dispersant having an alkylammonium salt structure, it was found that aggregated foreign matters derived from silica particles can be significantly suppressed. This is presumably because the silanol groups present on the surface of silica particles are effectively protected by the above dispersant, improving the dispersion stability in the photosensitive composition for black resist.

[0126] As shown in Examples 1 to 10, the ratio (m E / m F ) of the total mass (m F ) of the (F) dispersant to the total mass (m E ) of the (E) silica particles is set to 0.02 to 0.6, whereby it is possible to suppress the aggregated foreign matters derived from silica particles while suppressing the reflectance on the glass substrate side to 5% or less. If m F / m E is smaller than the above range, the dispersion stability of silica particles is insufficient and aggregated foreign matters are generated. On the other hand, if m F / m E is larger than the above range, the compatibility of silica particles becomes too high, so they do not unevenly distribute near the glass substrate, and the reflectance on the glass substrate side becomes larger than 5%.

Industrial Applicability

[0127] According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition for a black matrix that achieves both high light-shielding properties and low reflectance, a light-shielding film using the same, a color filter, and a touch panel. Further, according to this color filter and touch panel, it is possible to provide various display devices having excellent visibility.

Claims

1. (A) An unsaturated group-containing photosensitive resin, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) A photoinitiator, (D) At least one light-shielding component selected from the group consisting of a black pigment, a mixed-color pigment, and a light-shielding material, (E) Silica particles, (F) A dispersant, and containing, The (F) dispersant has an acid value and an amine value, both of which are 10 mgKOH / g or more and 80 mgKOH / g or less, and the total mass (m Ｅ ) of the (E) silica particles to the total mass (m Ｆ ) of the (F) dispersant, the ratio (m Ｆ / m Ｅ ) is 0.02 to 0.60, The content of the (E) silica particles is 0.1 to 5 parts by mass with respect to the total mass of the photosensitive resin composition containing a solvent, a photosensitive resin composition for black resist.

2. The (A) unsaturated group-containing photosensitive resin is an unsaturated group-containing photosensitive resin obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (1) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride, The photosensitive resin composition for black resist according to Claim 1. 【Chemical 1】 (In formula (1), R １ , R ２ , R ３ and R ４ are each independently either a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, 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 the general formula (2), or a single bond, and l is an integer of 0 to 10.)​​​ [Chemical Formula 2]

3. The (F) dispersant is a polymer compound having an alkylammonium salt structure, The photosensitive resin composition for black resist according to Claim 1 or Claim 2.

4. The average particle diameter of the (E) silica particles is 1 to 100 nm, The photosensitive resin composition for black resist according to any one of Claims 1 to 3.

5. The total mass (m Ｄ of the (E) silica particles with respect to the total mass (m Ｅ of the (D) light-shielding component is in the ratio (m Ｅ / m Ｄ ) of 0.01 to 0.

20. The photosensitive resin composition for black resist according to any one of claims 1 to 4.

6. (A) An unsaturated group-containing photosensitive resin, (B) A photopolymerizable compound having at least two or more unsaturated bonds, (C) A photoinitiator, (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, (E) A silica particle dispersion in which silica particles are dispersed in a solvent, In a method for producing a photosensitive resin composition for black resist, which is mixed, The (E) silica particle dispersion contains (F) a dispersant, The (F) dispersant has an acid value and an amine value, both the acid value and the amine value are 10 mgKOH / g or more and 80 mgKOH / g or less, and the total mass (m Ｅ ) of the (E) silica particles in the photosensitive resin composition for black resist, the ratio (m Ｆ ) of the total mass (m Ｆ / m Ｅ ) of the (F) dispersant is 0.02 to 0.60, The content of the (E) silica particles is 0.1 to 5 parts by mass with respect to the total mass of the photosensitive resin composition containing a solvent, A production method.

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.

10. A display device having the color filter according to Claim 8 or the touch panel according to Claim 9.

Images