TWI875825B - Photosensitive resin composition for black resist, manufacturing method of that, light-shielding film cured the same, color filter and touch panel having that film, display device having them - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition for black resist, which has high light-shielding property and low reflectance and is capable of forming a high-definition pattern.

The photosensitive resin composition for black resist of the present invention comprises: (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) aphotopolymerization initiator, (D) at least one light-shielding component selected from black pigments, mixed color pigments and light-shielding materials, (E) silica particles, and (F) a phosphate ester-based dispersant.

Description

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

The present invention relates to a photosensitive resin composition for black resist and a method for manufacturing the photosensitive resin composition, a light-shielding film formed 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.

In recent years, with the development of portable terminals, the number of display devices such as touch panels and liquid crystal panels used outdoors or in vehicles has gradually increased. In the above-mentioned display device, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the periphery of the rear liquid crystal panel. In order to suppress light leakage when displaying black and suppress color mixing between adjacent color resists, a black matrix is provided in the above-mentioned liquid crystal panel.

In display devices, etc., in order to suppress light leakage and improve the visual confirmation of the screen of the above-mentioned display devices, the black pigment concentration in the light-shielding film is increased, and the light-shielding property of the light-shielding film is improved (the light transmittance of the light-shielding film is reduced). Compared with the refractive index of the transparent substrate or the curing resin, the refractive index of the black pigment is higher. Therefore, if the black pigment concentration in the light-shielding film is increased, the reflectivity when viewed from the opposite side of the transparent substrate and the light-shielding film forming surface will increase. Therefore, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate will increase, resulting in undesirable situations such as being reflected on the light-shielding film or making the black matrix boundary more obvious due to the difference in reflectivity with the colored part of the color filter.

Therefore, a photosensitive resin composition for black resist having both high light-shielding properties and low reflectivity, a light-shielding film formed by curing the composition, and a color filter are required.

For example, Patent Document 1 discloses a black photosensitive resin composition containing hydrophobic silica particles and a specific dispersant (urethane-based dispersant). By using hydrophobic silica particles and a specific dispersant, a black matrix with high light-shielding properties and low reflectivity can be formed.

[Prior Art Literature]

[Patent Literature]

Patent document 1: Japanese Patent Publication No. 2015-161815.

However, the inventors of the present invention have found through review that the black photosensitive resin composition described in Patent Document 1 cannot obtain a light-shielding film having both the desired light-shielding property and reflectivity. In addition, the black photosensitive resin composition described in Patent Document 1 may produce saw-like shapes at the edges of the pattern when forming a pattern, or may produce residues derived from silicon dioxide particles on the substrate.

The present invention is completed in view of this point, and its purpose is to provide a photosensitive resin composition for black resist that has high light-shielding property and low reflectivity and can form a high-precision pattern, and a light-shielding film formed by curing the light-shielding film, a color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel.

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

In the method for producing a photosensitive resin composition for black resist of the present invention, the method for producing a photosensitive resin composition for black resist comprises mixing (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component dispersion formed by dispersing a light-shielding component in a solvent, and (E) a silicon dioxide particle dispersion formed by dispersing silicon dioxide particles in a solvent, and the aforementioned (E) silicon dioxide particle dispersion contains (F) a phosphate-based dispersant.

The light-shielding film of the present invention is formed by hardening the above-mentioned black resist with a photosensitive resin composition.

The color filter of the present invention has the above-mentioned light-shielding film as a black matrix.

The touch panel of the present invention has the above-mentioned light-shielding film as a black matrix.

The display device of the present invention has the above-mentioned color filter or the above-mentioned touch panel.

According to the present invention, a photosensitive resin composition for black resist having high light-shielding property and low reflectivity and capable of forming high-precision patterns, 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 and the touch panel can be provided.

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

1. (A) Ingredients

The photosensitive resin containing unsaturated groups belonging to component (A) of this embodiment preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkaline solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. If it is the above resin, there is no particular limitation and it can be widely used.

Examples of the above-mentioned photosensitive resin containing an unsaturated group include: an epoxy compound having two epoxypropyl ether groups derived from bisphenols (hereinafter referred to as "bisphenol-type epoxy compound represented by general formula (1)") is reacted with (meth)acrylic acid, and then the obtained compound having a hydroxyl group is reacted with a polycarboxylic acid or its anhydride to obtain an epoxy (meth)acrylate acid adduct. The epoxy compound derived from bisphenols refers to an epoxy compound obtained by reacting bisphenols with epoxyhalogen propane or its equivalent. In addition, "(meth)acrylic acid" is a collective name for acrylic acid and methacrylic acid, which is one or both of them.

The photosensitive resin containing unsaturated groups belonging to component (A) is preferably a bisphenol-type epoxy compound represented by general formula (1).

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently 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-, fluorene-9,9-diyl represented by formula (2) or a single bond; 1 is an integer from 0 to 10.)

The bisphenol type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by the reaction of bisphenols and epichlorohydrin. The reaction is generally accompanied by the oligomerization of the diepoxypropyl ether compound to produce an epoxy compound having two or more bisphenol skeletons.

Examples of bisphenols used in the reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfate, bis(4-hydroxy-3,5-dimethylphenyl)sulfate, bis(4-hydroxy-3,5-dichlorophenyl)sulfate, 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) 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( 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Among them, the preferred ones are bisphenols having fluorene-9,9-diyl.

Examples of the (a) dicarboxylic acid or tricarboxylic acid anhydride to be reacted with the hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting the epoxy compound with (meth)acrylic acid include: anhydrides of chain alkyl dicarboxylic acids or tricarboxylic acids, anhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and anhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of the chain alkyl dicarboxylic acids or tricarboxylic acids include: anhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, hydroxyglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Also included are anhydrides of dicarboxylic acids or tricarboxylic acids into which any substituents are introduced. In addition, examples of the acid monoanhydride of alicyclic dicarboxylic acids or tricarboxylic acids include: cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid and the like. In addition, the acid monoanhydride of dicarboxylic acids or tricarboxylic acids introduced with any substituents is also included. In addition, examples of the acid monoanhydride of aromatic dicarboxylic acids or tricarboxylic acids include: phthalic acid, isophthalic acid, trimellitic acid and the like. In addition, the acid monoanhydride of dicarboxylic acids or tricarboxylic acids introduced with any substituents is also included.

In addition, the (b) tetracarboxylic acid dianhydride to be reacted in the epoxy (meth)acrylate is a dianhydride of a chain alkyl tetracarboxylic acid, a dianhydride of an alicyclic tetracarboxylic acid, or an aromatic tetracarboxylic acid. Here, the dianhydride of the chain alkyl tetracarboxylic acid includes, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like, and may also be a dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein. In addition, the dianhydride of the alicyclic tetracarboxylic acid includes, for example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like, and may also be a dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein. In addition, the dianhydride of aromatic tetracarboxylic acid includes, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, etc., and may also be the dianhydride of tetracarboxylic acid introduced with any substituent.

The molar ratio (a)/(b) of the anhydride of (a) dicarboxylic acid or tricarboxylic acid and (b) tetracarboxylic acid dianhydride reacted in epoxy (meth)acrylate is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a)/(b) exceeds the above range, the optimal molecular weight for forming a photosensitive resin composition with good photopatterning properties cannot be obtained, so it is not good. In addition, the smaller the molar ratio (a)/(b), the larger the molecular weight, and there is a tendency for the alkali solubility to decrease.

Furthermore, the reaction of epoxy compounds with (meth) acrylic acid and the reaction of epoxy (meth) acrylate obtained by the reaction with polycarboxylic acid or its anhydride are not particularly limited, and known methods can be used. Furthermore, the weight average molecular weight (Mw) of the photosensitive resin containing unsaturated groups synthesized by the above reaction is preferably 2000 to 10000, and the acid value is preferably 30 to 200 mg/KOH.

Other preferred examples of the photosensitive resin containing an unsaturated group belonging to the component (A) include copolymers of (meth)acrylic acid, (meth)acrylates, etc., which include resins having (meth)acryloyl groups and carboxyl groups. Examples of the above resins include alkali-soluble resins containing polymerizable unsaturated groups obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent, reacting the resulting copolymer with (meth)acrylic acid, and finally reacting with anhydrides of dicarboxylic acids or tricarboxylic acids. The above copolymer can refer to the copolymer described in Japanese Patent Publication No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol whose two terminal hydroxyl groups 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 has a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g; and the polymerized unsaturated group-containing alkali-soluble resin described in Japanese Patent Publication No. 2018-141968, which includes units derived from (meth) acrylic acid ester compounds, and units having (meth) acryl groups and di- or tricarboxylic acid residues, and has a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mg/KOH.

The photosensitive resin containing unsaturated groups in component (A) may be used alone or in combination of two or more.

2. (B) Ingredients

Examples of the photopolymerizable monomer having at least two unsaturated bonds in the component (B) of 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, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane 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, phosphazene epoxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates, as well as dendrimers having (meth)acryloyl groups as compounds having ethylenic double bonds. These monomers may be used alone or in combination of two or more. Furthermore, the photopolymerizable monomer having at least two ethylenic unsaturated bonds can crosslink the molecules containing the alkali-soluble resin. In order to exert this function, it is preferred to use one having three or more unsaturated bonds. Furthermore, the acrylic acid equivalent obtained by dividing the monomer molecular weight by the number of (meth)acrylic groups in one molecule is preferably 50 to 300, and the acrylic acid equivalent is more preferably 80 to 200. Furthermore, component (B) does not have a free carboxyl group.

Examples of dendrimers having (meth)acryloyl groups of compounds having unsaturated bonds that can be contained in the composition as component (B) include dendrimers obtained by adding a polyvalent alkyl compound to a portion of the carbon-carbon double bonds in the (meth)acryloyl groups of polyfunctional (meth)acrylates. Specifically, the examples include dendrimers obtained by reacting the (meth)acryloyl groups of polyfunctional (meth)acrylates represented by general formula (3) with the polyvalent alkyl compounds represented by general formula (4).

(In formula (3), _R5 is a hydrogen atom or a methyl group, and _R6 is the portion of k hydroxyl groups of _R7 (OH) _k which is left after n hydroxyl groups are donated to the ester bond in the formula. Preferably, _R7 (OH) _k is a polyol based on a non-aromatic straight or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyol ether formed by dehydration condensation of a plurality of molecules of the polyol and linked through an ether bond, or an ester of the polyol or polyol ether with a hydroxy acid. k and n independently represent integers from 2 to 20, but k≧n.)

(In formula (4), _R8 is a single bond or a divalent to hexavalent alkyl group having 1 to 6 carbon atoms, and m is 2 when _R8 is a single bond, and has the same valence as _R8 when _R8 is a divalent to hexavalent group.)

Examples of the multifunctional (meth)acrylate represented by general formula (3) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate and the like (meth)acrylates. These compounds may be used alone or in combination of two or more.

Examples of the polyvalent alkyl compounds represented by general formula (4) include: trihydroxymethylpropane tri(alkyl acetate), trihydroxymethylpropane tri(alkyl propionate), pentaerythritol tetra(alkyl acetate), pentaerythritol tri(alkyl acetate), pentaerythritol tetra(alkyl propionate), dipentaerythritol hexa(alkyl acetate), dipentaerythritol hexa(alkyl propionate), etc. These compounds may be used alone or in combination of two or more.

The blending ratio of component (A) to component (B) is preferably 30/70 to 90/10, more preferably 60/40 to 80/20, in terms of weight ratio (A)/(B). If the blending ratio of component (A) is 30/70 or more, the cured product after photocuring is not easy to become brittle, and the acid value of the coating in the unexposed part is not easy to become low, so the reduction of solubility in alkaline developer can be suppressed. Therefore, it is less likely to produce undesirable situations such as the edge of the pattern becoming jagged or the inability to form a sharp pattern. In addition, if the blending ratio of component (A) is less than 90/10, the proportion of photoreactive functional groups in the resin is sufficient, so the desired cross-linked structure can be formed. In addition, the acid value of the resin component will not be too high, so the solubility of the exposed part relative to the alkaline developer is not easy to increase, so the formed pattern can be prevented from being thinner than the target line width or pattern defects.

3. (C) Ingredients

Examples of the photopolymerization initiator (C) of the present embodiment include: acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, diphenyl ketones such as 2-chlorophenyl ketone, p,p'-bisdimethylaminophenyl ketone, diphenyl ketones such as diphenyl ketone, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin ethers; 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-triaryl biphenyl imidazole and other biimidazole compounds; halogenated methyl thiazole compounds such as 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-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, 2-(4-methyl 2-(4-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiophenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Halogenated methyl-S-triazine compounds such as 1,3,5-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylthiohydrogenphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiohydrogenphenyl)butane-1,2-dione-2-oxime-O- O-acyl oxime compounds such as acetate, 1-(4-methylthiothiophenyl)butane-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O- acetyl oxime; diphenylethylenedione dimethyl ketal, thiothione, 2-chlorothiothione, 2,4-diethylthiothione, 2-methylthiothione, Sulfur compounds such as 2-isopropylthioxanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and isopropylbenzene peroxide; thiol compounds such as 2-butylbenzimidazole, 2-butylbenzoxazole, and 2-butylbenzothiazole, and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators can be used alone or in combination of two or more.

Examples of O-acyl oxime compounds that can be preferably used include O-acyl oxime photopolymerization initiators represented by general formula (5) and general formula (6). Among these compounds, when the light-shielding component is used at a high concentration, it is preferred to use an O-acyl oxime photopolymerization initiator having a molar absorption coefficient of 10,000 or more at 365 nm. In addition, the "photopolymerization initiator" described in the present invention contains a sensitizer.

(In formula (5), _R9 and _R10 independently represent 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 _R11 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen. The alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of a linear, branched, or cyclic alkyl group.)

(In formula (6), _R12 and _R13 are independently a linear or branched alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group, cycloalkylalkyl group or alkylcycloalkyl group having 4 to 10 carbon atoms; or a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms. _R14 is independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a portion of the _-CH2- groups in the alkyl group or alkenyl group may be substituted by an -O- group. Furthermore, a portion of the hydrogen atoms in the groups of _R12 to _R14 may be substituted by a halogen atom.)

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

4. (D) Ingredients

As the light-shielding components such as black pigment, mixed color organic pigment and light-shielding material belonging to the component (D) of this embodiment, as long as they are dispersed with an average particle size of 1 to 1000nm (average particle size 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 special restrictions.

Examples of black pigments belonging to component (D) include: perylene black, indigo black, aniline black, lactamide black, carbon black, titanium black, etc.

Examples of mixed color organic pigments of component (D) include: pigments mixed with at least two colors selected from azo pigments, condensed azo pigments, methine azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolone pigments, isoindolline pigments, bisoxizone pigments, reduced pigments, perylene pigments, peroxycyclic ketone pigments, quinoline yellow pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and other organic pigments.

The above-mentioned (D) component may be used alone or in combination of two or more, depending on the function of the intended photosensitive resin composition.

In addition, when using mixed color organic pigments as component (D), examples of organic pigments that can be used include those with the following numbers as indicated by the color index names, but are not limited to these.

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.;

Color orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;

Yellow pigment 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 purple 19, 23, 37, etc.

The blending ratio of the light-shielding component of the component (D) can be arbitrarily determined according to the desired light-shielding degree, but is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, relative to the solid content in the photosensitive resin composition. When an organic pigment such as aniline black, indigo black, beta-lactam black, or a carbon-based light-shielding component such as carbon black is used as the light-shielding component of the component (D), it is particularly preferably 40 to 60% by mass relative to the solid content in the photosensitive resin composition. If the light-shielding component is 20% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. If the light-shielding component is less than 80% by mass relative to the solid content in the photosensitive resin composition, the content of the photosensitive resin that will originally become the binder will not decrease, so the desired developing characteristics and film-forming ability can be obtained.

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

Examples of dispersants include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersing aids). In particular, in terms of adsorption points for colorants, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amine group, and an amine value of 1 to 100 mgKOH/g and a number average molecular weight (Mn) of 1000 to 100000. The blending amount of the dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass relative to the light-shielding component. Also, high-viscosity materials such as resins generally have the function of stabilizing dispersion, but those that do not have the ability to promote dispersion are not used as dispersants. However, there is no restriction on using them for the purpose of stabilizing dispersion.

Furthermore, the ratio (m _E /m D ) of the mass (m _E ) of the (E) silicon dioxide particles (described later) to the total mass (m _D ) of the light-shielding component ( _D ) is preferably 0.01 to 0.20, more preferably 0.05 to 0.1. If the ratio of the mass (m _E ) of the (E) silicon dioxide particles to the total mass (m _D ) of the light-shielding component (D) is within the above range, both high light-shielding property and low reflectivity can be achieved.

5. (E) Ingredients

The silicon dioxide particles belonging to the component (E) are manufactured by a manufacturing method such as gas phase reaction or liquid phase reaction, and there is no particular limitation on their shape (spherical, non-spherical).

The type of silica particles used in the present invention as component (E) is not particularly limited. Solid silica particles or hollow silica particles can be used. In addition, "hollow silica particles" refer to silica particles with a cavity inside the particle.

By using the above-mentioned silica particles, the refractive index of the light-shielding film containing the silica particles can be reduced.

The average particle size of the above-mentioned silica particles is preferably 1 to 100 nm, and more preferably 10 to 90 nm. Compared with the case of a small particle size of several nm, silica particles in the above-mentioned size range are less likely to agglomerate with each other. As a result, within the above-mentioned particle size range, the dispersion stability of the silica particles is excellent, so they can be uniformly present in the light-shielding film. Therefore, it is less likely to produce inconsistent reflectivity on the light-shielding film.

Furthermore, the content of the above-mentioned silica particles is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to the total mass of the photosensitive resin composition. If the content of the silica particles is within the above range, low reflectivity can be achieved and good patterning properties can be ensured.

The average particle size of the above-mentioned silicon dioxide particles can be measured by the cumulative method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using the dynamic light scattering method.

Furthermore, the above-mentioned silica particles may have a refractive index of 1.10 to 1.47. In addition to using general silica particles with a refractive index of 1.45 to 1.47, by using hollow silica particles with a low refractive index, the refractive index of the light-shielding film can be made lower than the refractive index of the light-shielding film containing only general silica particles.

In addition, the refractive index of the silica particles can be obtained by mixing the silica particles processed into powder with a standard refractive liquid of known refractive index to obtain a transparent mixed liquid. In this case, the refractive index of the standard refractive liquid of the mixed liquid is the refractive index of the silica particles. In addition, the refractive index of the silica particles can be measured using an Abbe refractometer.

In addition, since the reflection caused by the refractive index difference between the transparent substrate and the formed light-shielding film can be suppressed, the reflection can be suppressed without setting an anti-reflection film on the substrate.

The shape of the above-mentioned silicon dioxide particles can be a perfect circle or an ellipse. The shape of the silicon dioxide particles used in the present invention is preferably a perfect circle.

The roundness of the above-mentioned silica particles is preferably 1.0 to 1.5. If the roundness of the silica particles is within this range, the particle shape will be close to a perfect circle. Therefore, it can be uniformly filled in a thin light-shielding film, and a light-shielding film can be formed that maintains the smoothness of the film surface and does not expose the above-mentioned silica particles from the film surface to the outside. Therefore, a light-shielding film with a low refractive index and sufficient strength can be obtained.

The roundness of the above-mentioned silica particles can be obtained by the ratio of the longest diameter to the shortest diameter of the particles (the average value of any 100 silica particles). Here, the longest diameter and the shortest diameter of the silica particles are the values obtained by measuring the longest diameter and the shortest diameter of the silica particles from the microscope photographs obtained by photographing the silica particles with a transmission electron microscope.

The silica particles belonging to the component (E) can be mixed with other blending components as a silica particle dispersion dispersed in a solvent. The dispersant can be a known compound used for dispersing pigments (light-shielding components) (compounds commercially available under the names of dispersants, dispersing wetting agents, dispersing accelerators, etc.), etc., without any particular limitation. In this embodiment, the dispersant contained in the silica particle dispersion is preferably a (F) phosphate-based dispersant (described later).

6. (F) Ingredients

Examples of (F) phosphate ester dispersants of this embodiment include: phosphate monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, phosphate diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, phosphate triesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, alkyl phosphates, alkyl ether phosphates or their derivatives. The alkyl groups of the above-mentioned phosphate ester surfactants include styrenated phenol, nonylphenol, lauryl alcohol, tridecanol, octylphenol, etc.

Examples of commercially available phosphate dispersants include: ADEKA COL (TS-230E, CS-141E, CS-1361E, CS-279, PS-440E, PS-810E, PS-807, PS-984: all manufactured by ADEKA Co., Ltd., "ADEKA COL" is a registered trademark of the same company), Plysurf (A208B, A208F, A208N, A219B, DB-01, M208F: all manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., "Plysurf" is a registered trademark of the same company), 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 same company), etc. Among the above commercial products, the better ones are ADEKA COL TS-230E, CS-141E, PS-440E, and the more preferred one is ADEKA COL TS-230E.

(F) The content of the phosphate dispersant is preferably 0.05 to 0.5 parts by weight relative to the total weight of the photosensitive resin composition.

Furthermore, the ratio (m _F /m E ) of the mass (m _F ) of the above-mentioned (F) phosphate ester dispersant to the total mass (m _E ) of the above-mentioned (E) silicon dioxide particles is preferably 0.1 to 1.0, and more preferably 0.2 to 0.8. If the ratio of the mass (m _F ) of the above-mentioned ( _F ) phosphate ester dispersant to the total mass (m _E ) of the silicon dioxide particles is within the above-mentioned range, the jagged shape of the pattern edge and the residues on the substrate originating from the silicon dioxide particles can be suppressed, and a high-precision pattern can be formed.

The above-mentioned components (A) to (F) are mixed and dispersed by an appropriate method to prepare the dispersion used in the photosensitive resin composition of the present invention.

7.Solvent

In addition to the components (A) to (F) in the photosensitive resin composition of the present invention, it is preferred to use a solvent belonging to 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; cellosol, methylcellosol, ethylcellosol, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether; , propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosol acetate, ethyl cellosol acetate, butyl cellosol acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other acetates. These can be dissolved and mixed alone or in combination of two or more to form a uniform solution composition.

In addition, the photosensitive resin composition of the present invention may be blended with resins other than component (A) such as epoxy resin, hardener, hardening accelerator, thermal resistance polymerization agent and antioxidant, plasticizer, filler other than silica, leveling agent, defoaming agent, surfactant, coupling agent and other additives as needed.

Examples of heat-resistant polymers and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylpyrogallol, phenothiazine, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silicon dioxide, mica, aluminum oxide, etc. Examples of defoamers or leveling agents include silicone, fluorine, and acrylic compounds. Examples of surfactants include fluorine surfactants, silicone surfactants, etc. Examples of coupling agents include: 3-(epoxypropyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The photosensitive resin composition of the present invention preferably contains a photosensitive resin containing an unsaturated group as component (A), a photopolymerizable monomer having at least two unsaturated bonds as component (B), a photopolymerization initiator as component (C), at least one light-shielding component selected from black pigment, mixed color pigment and light-shielding material as component (D), (E) silicon dioxide particles, and (F) a phosphate-based dispersant in the solid matter (including monomers that become solid matter after curing) after removing the solvent. The amount of solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass relative to the total amount.

The photosensitive resin composition of the present invention can be prepared by mixing (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component dispersion obtained by dispersing a light-shielding component in a solvent, and (E) a silica particle dispersion obtained by dispersing silica particles in a solvent to produce a photosensitive resin composition for a black resist. The above-mentioned (E) silica particle dispersion contains (F) a phosphate-based dispersant.

By making the (E) silica particle dispersion contain (F) a phosphate-based dispersant in advance, the storage stability of the silica dispersion can be improved and the generation of agglomerates can be prevented when mixed with other resin components.

In addition, the light-shielding film formed 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, drying the solvent, and irradiating light (including ultraviolet rays, radiation, etc.) to cure. By using a photomask, etc. to set the illuminated part and the unilluminated part, only the illuminated part is cured, and the other parts are dissolved with an alkaline solution, the desired pattern can be obtained.

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

In addition, the light-shielding film formed by curing the photosensitive resin composition of the present invention can be used as a black column spacer for a liquid crystal display device. For example, a single black resist can be used to make multiple portions with different film thicknesses, one side of which functions as a spacer and the other side functions as a black matrix.

The steps of the film-forming method for coating and drying a photosensitive resin composition to form a light-shielding film are specifically described.

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

The radiation used for exposure may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., and the wavelength range of the radiation is preferably 250 to 450 nm. In addition, the developer suitable for the alkaline development may be, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. The developer may be appropriately selected in accordance with the properties of the resin layer, but it is also effective to add a surfactant as needed. The developing temperature is preferably 20 to 35°C, and a commercially available developer or ultrasonic cleaner may be used to precisely form a microscopic image. In addition, water washing is usually performed after alkaline development. The developing method can use shower developing method, spray developing method, immersion developing method, paddle developing method (liquid filling) developing method, etc.

After such development, heat treatment (post-baking) is performed at 180 to 250°C for 20 to 100 minutes. The purpose of the post-baking is to improve the adhesion between the patterned hardened film (light-shielding film) and the substrate. This is performed by heating in an oven, a heating plate, etc., similar to pre-baking. The patterned hardened film (light-shielding film) of the present invention is formed through various steps of photolithography. Then, polymerization or hardening (both are collectively referred to as hardening) is terminated by heat, and a light-shielding film with the desired pattern can be obtained. The curing temperature at this time is preferably 160 to 250°C.

As mentioned above, the black resist photosensitive resin composition of the present invention is not only suitable for forming fine patterns through exposure, alkaline development and other operations, but also can obtain a light-shielding film with the same excellent light-shielding properties, adhesion, electrical insulation, heat resistance and chemical resistance even if the pattern is formed by conventional screen printing.

The photosensitive resin composition for black resist of the present invention is suitable for use as a coating material. In particular, it can be used as a color filter ink used in a liquid crystal display device or a camera element, and the light-shielding film formed thereby can be used as a color filter, a black matrix for liquid crystal projection, etc. In addition, the photosensitive resin composition for black resist of the present invention can be used as a color filter ink for a color liquid crystal display, and can also be used as a color-differentiating or light-shielding ink material in various multicolor display bodies such as organic electroluminescent devices represented by organic EL elements, color liquid crystal display devices, color facsimile, and image sensors. The color filter according to the present invention can reduce the external light reflection at the interface between the coloring layer (including the black resist layer) and the substrate, or the light reflection from the element when used in an organic EL element. That is, it is possible to improve the contrast of bright areas by reducing external light reflection, or to improve the efficiency of light extraction from the light-emitting side to improve the luminous efficiency.

(Implementation example)

The following is a detailed description of the implementation of the present invention based on embodiments and comparative examples, but the present invention is not limited to them.

First, the synthesis examples of the alkali-soluble resin containing polymerizable unsaturated groups belonging to component (A) are described. However, the evaluation of the resin in these synthesis examples is carried out in the following manner unless otherwise specified.

[Solid concentration]

1 g of the resin solution obtained in the Synthesis Example was impregnated in a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)]. The weight after heating at 160°C for 2 hours [W ₂ (g)] was determined by the following formula.

Solid content (weight %) = 100 × (W ₂ -W ₀ ) / (W ₁ -W ₀ )

[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.).

[Molecular weight]

The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pieces) + TSKgelSuper H-3000 (1 piece) + TSKgelSuper H-4000 (1 piece) + TSKgelSuper H-5000 (1 piece) (manufactured by TOSOH Co., Ltd.), temperature: 40°C, speed: 0.6 ml/min) and converted to standard polystyrene (PS-Oligomer Kit manufactured by TOSOH Co., Ltd.).

[Average particle size]

The average particle size of the silicon dioxide particles was obtained by the cumulative method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using the dynamic light scattering method.

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

BPFE: a product of the reaction of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of the general formula (1) wherein X is fluorene-9,9-diyl and _R1 to _R4 are hydrogen.

DCPMA: dicyclopentyl 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: tris(dimethylaminomethyl)phenol.

HQ: Hydroquinone.

TEA: triethylamine.

PGMEA: Propylene glycol monomethyl ether acetate.

[Synthesis Example 1]

BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were added to a 500 ml four-necked flask with a reflux cooler, and stirred at 100 to 105°C for 20 hours. Then BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask, and stirred at 120 to 125°C for 6 hours to obtain an alkali-soluble resin (A)-1 containing polymerizable unsaturated groups. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw of GPC analysis was 3600.

[Synthesis Example 2]

PGMEA (300 g) was added to a 1L four-necked flask with a reflux cooler, and the flask system was replaced with nitrogen and the temperature was raised to 120°C. A mixture of AIBN (10 g) dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol) was dripped into the flask from a dropping funnel over 2 hours, and further stirred at 120°C for 2 hours to obtain a copolymer solution.

Then, after replacing the air in the flask system with air, AA (24.0 g, 95% of propylene oxide), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and stirred at 120°C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups. SA (30.0 g, 90% of the molar number of AA added) and TEA (0.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and reacted at 120°C for 4 hours to obtain an alkali-soluble resin (A)-2 containing unsaturated groups. The solid content concentration of the resin solution was 46.0% by mass, the acid value (solid content conversion) was 76 mgKOH/g, and the Mw of GPC analysis was 5300.

The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared with the blending amounts (in mass %) listed in Table 1. The blending ingredients used in the table are as follows.

(Alkaline soluble resin containing polymerizable unsaturated groups)

(A)-1: Alkaline soluble resin solution obtained in the above-mentioned Synthesis Example 1 (solid content concentration 56.1 mass %).

(A)-2: Alkaline soluble resin solution obtained in the above-mentioned Synthesis Example 2 (solid content concentration 46.0 mass %).

(Photopolymerizable monomer)

(B): A mixture of dipentatriol hexaacrylate and dipentatriol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd., "Aronix" is a registered trademark of the same company).

(Photopolymerization initiator)

(C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime) (Irgacure OXE-02, manufactured by BASF JAPAN, "Irgacure" is a registered trademark of the same company).

(C)-2: ADEKA ARKLS NCI-831, manufactured by ADEKA Co., Ltd. "ADEKA ARKLS" is a registered trademark of the same company).

(Carbon black dispersion)

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

(E)-1: Silica PGMEA dispersion "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration 40% by mass, average particle size 50nm).

(E)-2: Silica PGMEA dispersion "YA010C" (manufactured by Admatechs Co., Ltd., solid content concentration 20% by mass, average particle size 10nm).

(E)-3: Silica PGMEA dispersion "YC100C" (manufactured by Admatechs Co., Ltd., solid content concentration 50% by mass, average particle size 100nm).

(Dispersant)

(F)-1: ADEKA COL TS-230E (manufactured by ADEKA Co., Ltd., "ADEKA COL" is a registered trademark of the same company).

(F)-2: ADEKA COL PS-440E (manufactured by ADEKA Co., Ltd.).

(F)-3: ADEKA COL CS-141E (manufactured by ADEKA Co., Ltd.).

(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 40% by mass).

In addition, (F)-1 to (F)-3 are phosphate-based dispersants, (F)-4 is a urethane-based dispersant, and (F)-5 is an acrylic-based dispersant.

(Solvent)

(G)-1: Propylene glycol monomethyl ether acetate (PGMEA).

(G)-2: Cyclohexanone (ANON).

[Table 1]

[Evaluation]

The black resist used for evaluation is hardened with a photosensitive resin composition to produce a hardened film (light shielding film) in the following manner.

(Production of hardened film (light-shielding film) for developing property evaluation)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet light of 1000 mJ/ ^cm2 at a wavelength of 254 nm by a low-pressure mercury lamp, and then applied using a rotary coater on a surface-cleaned 125 mm×125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as the "glass substrate") in such a manner that the film thickness after heat curing treatment becomes 1.2 μm, and then pre-baked at 90°C for 1 minute using a heating plate to prepare a hard film (light-shielding film). Then, the exposure gap is adjusted to 100μm, and a negative mask with line/space = 10μm/50μm is covered on the dry light-shielding film. An ultra-high pressure mercury lamp with an i-line illumination of 30mW/ ^cm2 is used to irradiate 50mJ/ ^cm2 of ultraviolet light to perform a photohardening reaction on the photosensitive part.

Next, the exposed cured film (light-shielding film) was developed by using a 0.04% potassium hydroxide solution at 25°C and a shower pressure of 1 kgf/ ^cm2 for +10 seconds and +20 seconds from the development time (cut-off time = BT) from the development of the pattern, and then washed with a spray water of 5 kgf/ ^cm2 to remove the unexposed portion of the cured film (light-shielding film), and a cured film pattern was formed on a glass substrate. A hot air dryer was used to perform main curing (post-baking) at 120°C for 60 minutes to obtain the cured films (light-shielding films) of Examples 1 to 9 and Comparative Examples 1 to 4.

The following items were evaluated for the cured films (light shielding films) formed by curing the black resist photosensitive resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4.

[Development characteristics evaluation]

(Linearity of pattern)

(Evaluation method)

The 10μm mask pattern of the main curing (post-baking) was observed using an optical microscope and a scanning electron microscope (SEM) to observe the sawtooth shape and residues from silicon dioxide particles at the edge of the pattern. In addition, the linearity evaluation of the pattern was performed at BT+10 seconds and BT+20 seconds. In addition, ○ or above is qualified.

(Evaluation criteria for developing characteristics)

○: No sawtooth shape was found on the edge of the pattern.

△: The sawtooth shape of some pattern edges is confirmed.

×: The sawtooth shape of the edge of the overall pattern is confirmed.

(Evaluation criteria for residue)

○: No residues derived from silicon dioxide particles were observed at the edge and opening of the pattern.

△: Residues from silica particles were partially observed at the edge and opening of the pattern.

×: Residues derived from silicon dioxide particles were observed at the edges and openings of the pattern.

[Optical density evaluation]

(Evaluation method)

The optical density (OD) of the produced cured film (light shielding film) was evaluated using a MACBETH density meter. In addition, the film thickness of the cured film (light shielding film) formed on the substrate was measured, and the value obtained by dividing the optical density (OD) value by the film thickness was taken as OD/μm.

Optical concentration (OD) is calculated using the following formula (1).

Optical concentration (OD) = -log ₁₀ T (1)

(T represents transmittance)

[Reflectivity evaluation]

(Evaluation method)

The reflectivity of the cured film (light shielding film) side and the substrate (glass substrate) side were measured at an incident angle of 2° using the UV-Vis-IR spectrophotometer "UH4150" (manufactured by Hitachi-Hightech Co., Ltd.) with respect to the substrate with a cured film (light shielding film) made with the optical density (OD) evaluation.

The above evaluation results are shown in Table 2.

[Table 2]

Compared to the system without silica particles (Comparative Example 1), the black resist photosensitive resin composition of Examples 1 to 9 can confirm that the reflectivity from the substrate side is reduced. In addition, compared to Comparative Examples 1 and 2 without adding dispersant or Comparative Examples 3 and 4 using urethane dispersant and acrylic dispersant, the black resist photosensitive resin composition of Examples 1 to 9 using phosphate dispersant can confirm that the linearity of the pattern and the residue on the substrate are good.

(Industrial availability)

According to the photosensitive resin composition of the present invention, a black matrix photosensitive resin composition having both high light-shielding property and low reflectivity, and a light-shielding film, a color filter, and a touch panel using the same can be provided. In addition, various display devices with excellent visual confirmation can be provided based on the color filter and the touch panel.

Claims (10)

A photosensitive resin composition for black resist contains: (A) a photosensitive resin containing an unsaturated group, (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 a black pigment, a mixed color pigment, and a light-shielding material, (E) silicon dioxide particles, and (F) a phosphate ester dispersant; wherein the phosphate ester dispersant (F) contains a phosphate monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, a phosphate diester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, a phosphate triester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, an alkyl phosphate, an alkyl ether phosphate, or a derivative thereof, and the alkyl group contains a styrenated phenol group, a nonylphenol group, a lauryl alcohol group, a tridecanol group, or an octylphenol group. The photosensitive resin composition for black resist as described in claim 1, wherein the photosensitive resin (A) containing an unsaturated group is a reaction product of an epoxy compound having two epoxypropyl ether groups derived from a bisphenol represented by the general formula (1) and (meth) acrylic acid, and further reacted with a polycarboxylic acid or its anhydride to obtain a photosensitive resin containing an unsaturated group.

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently 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 general formula (2) or a single bond, and l is an integer from 0 to 10

The photosensitive resin composition for black resist as claimed in claim 1 or claim 2, wherein the ratio (m F /m _{E ) of the mass (m F} ) of the aforementioned (F) phosphate ester dispersant to the total mass (m _E ) of the aforementioned ( _E ) silicon _dioxide particles is 0.1 to 1.0. The photosensitive resin composition for black resist as described in claim 1 or claim 2, wherein the average particle size of the aforementioned (E) silicon dioxide particles is 1 to 100 nm. The photosensitive resin composition for black resist as claimed in claim 1 or claim 2, wherein the ratio (m E /m _{D ) of the mass (m E )} of the aforementioned (E) silicon dioxide particles to the total mass (m _D ) of the aforementioned ( _D ) light-shielding component is 0.01 to 0.20. A method for producing a photosensitive resin composition for black resist, wherein the photosensitive resin composition for black resist is a mixture of (A) a photosensitive resin containing an unsaturated group, (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 silicon dioxide particle dispersion in which silicon dioxide particles are dispersed in a solvent, wherein the silicon dioxide particle dispersion (E) contains (F) a phosphate-based component. Powder; wherein the aforementioned (F) phosphate ester dispersant comprises a phosphate monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, a phosphate diester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, a phosphate triester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, an alkyl phosphate, an alkyl ether phosphate or a derivative thereof, wherein the aforementioned alkyl comprises a styrenated phenol system, a nonylphenol system, a lauryl alcohol system, a tridecanol system, or an octylphenol system. A light-shielding film is formed by hardening the black resist photosensitive resin composition as described in any one of claims 1 to 5. A color filter having a light-shielding film as described in claim 7 as a black matrix. A touch panel having a light shielding film as described in claim 7 as a black matrix. A display device having a color filter as described in claim 8 or a touch panel as described in claim 9.