TWI900597B - Photosensitive resin composition for black anti-etching agent, manufacturing method thereof, light-shielding film, color filter, touch panel and display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a black resist that exhibits high light-shielding properties and low reflectivity, enables the formation of fine patterns, and suppresses the formation of aggregated foreign matter. The photosensitive resin composition for a black resist disclosed herein comprises: (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 color-mixing pigment, and a light-shielding material; (E) silica particles; and (F) a dispersant. The (F) dispersant has an acid value and an amine value, both of which are 10 mgKOH/g or higher and 80 mgKOH/g or lower. The ratio (m _F /m _E ) 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.

Description

Photosensitive resin composition for black anti-etching agent, manufacturing method thereof, light-shielding film, color filter, touch panel and display device

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 formed by curing the photosensitive resin composition for a black resist, 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, the development of mobile devices has led to an increase in the use of display devices such as touch panels and liquid crystal panels for outdoor and automotive applications. In these display devices, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back. Furthermore, a black matrix is provided on the liquid crystal panel to suppress light leakage from the screen during black display and to prevent color mixing between adjacent color resists.

In displays and other devices, to reduce light leakage and improve screen visibility, the concentration of black pigment in a light-shielding film is sometimes increased to enhance the film's light-shielding properties (reduce the film's light transmittance). Because black pigment has a higher refractive index than the transparent substrate or curing resin, increasing the black pigment concentration in the light-shielding film increases the reflectivity when viewed from the side of the transparent substrate opposite the surface on which the light-shielding film is formed. This increases reflection at the interface between the light-shielding film and the transparent substrate, leading to undesirable issues such as reflections on the light-shielding film or a noticeable black matrix boundary caused by a difference in reflectivity with the colored portion of the color filter.

Therefore, there is an urgent need for a black resist photosensitive resin composition having both high light-shielding properties and low reflectivity, as well as a light-shielding film and a color filter formed by curing the composition.

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

[Patent Document 1] Japanese Patent Publication No. 2015-161815

[Problem to be Solved by the Invention] However, the inventors conducted research and discovered that the black photosensitive resin composition described in Patent Document 1 has the following problems: during pattern formation, the pattern edges become jagged, and aggregated foreign matter originating from silica particles forms on the black matrix.

The present invention was developed in light of the above-mentioned circumstances, and its object is to provide a photosensitive resin composition for a black anti-etching agent that has high light-shielding properties and low reflectivity, can form high-definition patterns, and can suppress the formation of aggregated foreign matter; a light-shielding film formed by curing the composition; a color filter and touch panel having the light-shielding film; and a display device having the color filter and touch panel. [Solution]

The photosensitive resin composition for a black anti-etching agent of the present invention comprises: (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 color-mixing pigment, and a light-shielding material, (E) silica particles, and (F) a dispersant. The dispersant (F) has an acid value and an amine value, each of which is 10 mgKOH/g or higher and 80 mgKOH/g or lower. The ratio ( _mF / _mE ) of the total mass ( _mF ) of the dispersant (F) to the total mass ( _mE ) of the silica particles (E) is 0.02 to 0.60.

The method for producing a photosensitive resin composition for a black resist of the present invention comprises mixing (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, a light-shielding component dispersion obtained by dispersing (D) a light-shielding component in a solvent, and a silica particle dispersion obtained by dispersing (E) silica particles in a solvent. In the method for producing a photosensitive resin composition for a black resist, the silica particle dispersion (E) contains a dispersant (F), the dispersant (F) having 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 _F ) of the dispersant (F) relative to the total mass (m E ) of the silica particles (E ₎ is 100 mgKOH/g or less. ) ratio (m _F /m _E ) is 0.02 to 0.60.

The light-shielding film of the present invention is formed by curing the black anti-etching agent with a photosensitive resin composition.

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

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

The display device of the present invention includes the color filter or the touch panel. [Effects of the Invention]

The present invention provides a photosensitive resin composition for a black anti-etching agent that has high light-shielding properties and low reflectivity, can form high-definition patterns, and can suppress the formation of aggregated foreign matter; a light-shielding film formed by curing the light-shielding film; a color filter and touch panel having the light-shielding film; and a display device having the color filter and touch panel.

The present invention is described in detail below. The photosensitive resin composition for a black resist (hereinafter referred to as the "photosensitive resin composition") of the present invention comprises (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 a black pigment, a color-mixing pigment, and a light-shielding material, (E) silica particles, and (F) a dispersant. Components (A) through (F) are described below.

1. Component (A) The unsaturated group-containing photosensitive resin serving as component (A) in this embodiment preferably contains, within a single molecule, a polymerizable unsaturated group and an acidic group for alkaline solubility. More preferably, it contains both a polymerizable unsaturated group and a carboxyl group. The resin is not particularly limited and can be used broadly as long as it is one of the above resins.

Examples of the unsaturated group-containing photosensitive resin include epoxy (meth)acrylate acid adducts obtained by reacting (meth)acrylic acid with an epoxy compound having two glycidyl ether groups derived from a bisphenol (hereinafter also referred to as a "bisphenol-type epoxy compound represented by general formula (1)") to obtain a compound having a hydroxyl group, and reacting a polycarboxylic acid or its anhydride with the obtained compound having a hydroxyl group. The epoxy compound derived from a bisphenol refers to an epoxy compound obtained by reacting a bisphenol with an epihalogen alcohol, or its equivalent. Furthermore, the term "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to one or both of these.

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

[Chemistry 1]

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom; 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)

[Chemistry 2]

The bisphenol-type epoxy compound represented by general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin. This reaction is usually accompanied by oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds containing 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)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)sulfone. phenyl)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-hydroxyphenyl) (4-Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9, 9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Among them, bisphenols having a fluorene-9,9-diyl group are preferred.

Examples of the (a) dicarboxylic acid or tricarboxylic acid monoanhydride that reacts with the hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include monoanhydrides of chain-type alkyl dicarboxylic acids or tricarboxylic acids, monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of the monoanhydride of chain-type alkyl dicarboxylic acids or tricarboxylic acids include monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. These also include monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituents have been introduced. Examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. These also include monoanhydrides of dicarboxylic acids or tricarboxylic acids that have any substituents introduced therein. Examples of monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, and trimellitic acid. These also include monoanhydrides of dicarboxylic acids or tricarboxylic acids that have any substituents introduced therein.

As the (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate, a chain alkyl tetracarboxylic acid dianhydride, an alicyclic tetracarboxylic acid dianhydride, or an aromatic tetracarboxylic acid dianhydride can be used. Examples of chain alkyl tetracarboxylic acid dianhydrides include butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid dianhydrides. Examples of these dianhydrides include tetracarboxylic acid dianhydrides with any substituent introduced therein. Examples of alicyclic tetracarboxylic acid dianhydrides include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid dianhydrides. Examples of these dianhydrides include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid dianhydrides. Furthermore, it includes dianhydrides of tetracarboxylic acids into which any substituents are introduced.

The molar ratio (a)/(b) of (a) the dicarboxylic acid or tricarboxylic acid monoanhydride and (b) the tetracarboxylic acid dianhydride reacted with the epoxy (meth)acrylate is preferably 0.01 to 10.0, more preferably 0.02 or greater and less than 3.0. A molar ratio (a)/(b) outside this range is not preferred because it fails to achieve the optimal molecular weight for producing a photosensitive resin composition with good photopatternability. Furthermore, as the molar ratio (a)/(b) decreases, the molecular weight increases, and the alkali solubility decreases.

The reaction of the epoxy compound with (meth)acrylic acid, and the reaction of the epoxy (meth)acrylate obtained by the reaction with a polycarboxylic acid or its anhydride, are not particularly limited, and known methods may be employed. The unsaturated group-containing photosensitive resin synthesized by the reaction preferably has a weight-average molecular weight (Mw) of 2,000 to 10,000 and an acid value of 30 to 200 mgKOH/g. The acid value can be determined by dissolving the resin solution in dioxane and titrating with a 1/10 N-KOH aqueous solution using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). The weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin can be measured using, for example, a gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation).

Other preferred examples of the unsaturated group-containing photosensitive resin as component (A) include copolymers of (meth)acrylic acid, (meth)acrylates, and the like, and having (meth)acryloyl and carboxyl groups. Examples of such resins include alkali-soluble resins containing polymerizable unsaturated groups obtained by copolymerizing (meth)acrylates including glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting (meth)acrylic acid with the resulting copolymer, and finally reacting with an anhydride of a dicarboxylic acid or tricarboxylic acid. The copolymers may refer to: a copolymer described in Japanese Patent Laid-Open No. 2014-111722, comprising 20 mol% to 90 mol% of repeating units derived from a diester glycerol obtained by esterifying the hydroxyl groups at both ends with (meth) acrylic acid, and 10 mol% to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 mgKOH/g to 120 mgKOH/g; and a copolymer described in Japanese Patent Laid-Open No. 2018-141968, comprising units derived from a (meth)acrylate compound and units having a (meth)acryloyl group and a dicarboxylic acid residue or a tricarboxylic acid residue, having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 mgKOH/g to 200 A polymer with a concentration of 1 mgKOH/g is an alkali-soluble resin containing polymerizable unsaturated groups.

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

2. Component (B) Examples of the photopolymerizable monomer having at least two unsaturated bonds as component (B) in this embodiment include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. (Meth)acrylates such as (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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and dendrimers containing (meth)acryloyl groups as compounds having ethylenic double bonds. These monomers may be used alone or in combination of two or more. The photopolymerizable monomer having at least two ethylenically unsaturated bonds can crosslink the molecules of the contained alkali-soluble resin. To achieve this function, it is preferred to use a monomer having three or more unsaturated bonds. Furthermore, the acrylic acid equivalent (acrylic acid equivalent), obtained by dividing the monomer's molecular weight by the number of (meth)acrylic acid groups per molecule, is preferably 50 to 300, and more preferably 80 to 200. Furthermore, component (B) does not contain free carboxyl groups.

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

[Chemistry 3]

(In formula (3), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the residue remaining after n hydroxyl groups among the k hydroxyl groups in R ₇ (OH) _k are donated to the ester bond in the formula; preferably, R ₇ (OH) _k is a polyol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyol ether in which multiple molecules of the polyol are linked via ether bonds by dehydration condensation of an alcohol, or an ester of these polyols or polyol ethers with a hydroxy acid; k and n independently represent integers of 2 to 20, and k ≧ n)

[Chemistry 4]

(In formula (4), _R8 is a single bond or a divalent to hexavalent alkyl group with 1 to 6 carbon atoms. 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 polyfunctional (meth)acrylate represented by general formula (3) include (meth)acrylates such as 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, and caprolactone-modified pentaerythritol tri(meth)acrylate. These compounds may be used alone or in combination of two or more.

Examples of the polyvalent alkyl compound represented by general formula (4) include trihydroxymethylpropane tris(alkyl acetate), trihydroxymethylpropane tris(alkyl propionate), pentaerythritol tetra(alkyl acetate), pentaerythritol tris(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 mixing ratio of components (A) and (B) is preferably 30/70 to 90/10, more preferably 60/40 to 80/20, as measured by weight (A)/(B). A mixing ratio of 30/70 or greater prevents the cured product from becoming brittle after photocuring. Furthermore, the acid value of the coating in the unexposed areas is less likely to decrease, thereby suppressing a decrease in solubility in alkaline developers. Consequently, undesirable issues such as jagged edges or blurred image quality are less likely to occur. Furthermore, a mixing ratio of 90/10 or less ensures a sufficient proportion of photoreactive functional groups in the resin, enabling the formation of the desired crosslinked structure. Furthermore, since the acid value of the resin component is not too high, the solubility of the exposed portion in the alkaline developer is unlikely to increase, thereby preventing the formed pattern from becoming thinner than the target line width or pattern loss.

3. Component (C) Examples of the photopolymerization initiator used as component (C) in this embodiment include: acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bis(dimethylaminobenzophenone); and benzoyl, anthracene, and benzophenone. Benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5- Biimidazole compounds such as triarylbiimidazoles; halogenated methylthiazole compounds such as 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 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, (4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 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 and other halogenated methyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O- O-acyl oxime compounds such as acetate, 1-(4-methylthiophenyl)butane-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyl oxime; benzyl dimethyl ketal, thioanthrone, 2-chlorothioanthrone, 2,4-diethylthioanthrone, 2-methylthioanthrone, 2-isothioanthrone Sulfur compounds such as propylthioanthrone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-benzylbenzimidazole, 2-benzylbenzoxazole, and 2-benzylbenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators can be used alone or in combination.

Examples of preferably used O-acyl oxime compound groups include O-acyl oxime photopolymerization initiators represented by the following general formula (5) and the following general formula (6). Among these compound groups, when using a light-shielding component at a high concentration, it is preferred to use an O-acyl oxime photopolymerization initiator having a molar extinction coefficient of 10,000 or greater at 365 nm. The term "photopolymerization initiator" as used in the present invention includes a sensitizer.

[Chemistry 5]

(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; _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; herein, 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 alkylyl 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; and the alkyl group may be any of a linear, branched, or cyclic alkyl group.)

[Chemistry 6]

(In formula (6), R ₁₂ and R ₁₃ are each 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 with an alkyl group having 1 to 6 carbon atoms; R ₁₄ is each independently a linear or branched alkyl group or an alkenyl group having 2 to 10 carbon atoms, wherein a portion of the -CH ₂ - groups in the alkyl or alkenyl groups may be substituted with -O- groups; furthermore, a portion of the hydrogen atoms in these R ₁₂ to R ₁₄ groups may be substituted with halogen atoms)

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

4. Component (D) The light-shielding component (D) of this embodiment, such as a black pigment, mixed color organic pigment, or light-shielding material, may be any known light-shielding component without particular limitation, as long as it is dispersed with an average particle size of 1 nm to 1000 nm (as measured using a laser diffraction/scattering particle size analyzer or a dynamic light scattering particle size analyzer).

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

Examples of the mixed color organic pigments used as component (D) include pigments obtained by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

Depending on the function of the target photosensitive resin composition, the component (D) may be used alone or in combination of two or more.

Furthermore, when using a mixed color organic pigment as component (D), examples of organic pigments that can be used include, but are not limited to, the pigments with the following numbers in the Color Index. 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: 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: 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.

The blending ratio of the light-blocking component (D) can be arbitrarily determined based on the desired light-blocking effect, but is preferably 20% to 80% by mass, and more preferably 40% to 70% by mass, relative to the solids content of the photosensitive resin composition. When using an organic pigment such as aniline black, cyanine black, or lactamide black, or a carbon-based light-blocking component such as carbon black, the light-blocking component (D) preferably contains 40% to 60% by mass, relative to the solids content of the photosensitive resin composition. A light-blocking effect can be achieved adequately when the light-blocking component accounts for 20% or more of the solids content of the photosensitive resin composition. If the light-shielding component is 80% by mass or less relative to the solid content in the photosensitive resin composition, the content of the photosensitive resin that originally serves as a binder will not be reduced, and thus desired developing characteristics and film-forming ability can be obtained.

Component (D) is typically mixed with the other ingredients in the form of a light-blocking component dispersion in a solvent. A dispersant may be added at this time. Dispersants can be used without particular limitation and include known compounds used for dispersing pigments (light-blocking components) (commercially available compounds known as dispersants, dispersing wetting agents, dispersion accelerators, etc.).

Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative-based dispersants (dispersing aids). In particular, from the perspective of colorant adsorption, cationic polymer dispersants are preferably those having cationic functional groups such as imidazole, pyrrolyl, pyridyl, primary, secondary, or tertiary amine groups, an amine value of 1 mgKOH/g to 100 mgKOH/g, and a number average molecular weight (Mn) of 1,000 to 100,000. The amount of the dispersant to be added is preferably 1% to 35% by mass, more preferably 2% to 25% by mass, relative to the light-blocking component. Furthermore, high-viscosity substances such as resins generally have the effect of stabilizing dispersion, but substances that do not promote dispersion are not considered dispersants. However, this does not limit the use of dispersants for the purpose of stabilizing dispersion.

Furthermore, the ratio (m _E /m _D ) of the total mass (m _E ) of the (E) silica particles (described below) to the total mass (m _D ) of the (D) light-shielding component is preferably 0.01 to 0.20, more preferably 0.05 to 0.1. When the ratio of the total mass (m _E ) of the (E) silica particles to the total mass (m _D ) of the (D) light-shielding component is within this range, both high light-shielding properties and low reflectivity can be achieved.

5. Component (E) Regarding the silica particles used as component (E), there are no particular restrictions on the production method (e.g., vapor phase reaction or liquid phase reaction) or the shape (spherical or non-spherical).

The type of silica particles used as component (E) in the present invention is not particularly limited. Both solid and hollow silica particles can be used. "Hollow silica particles" refer to silica particles with a cavity inside.

By using the silica particles, the refractive index of the light-shielding film including the silica particles can be lowered.

The average particle size of the silica particles is preferably 1 nm to 100 nm, more preferably 10 nm to 90 nm. It is believed that particles within this range are less likely to aggregate, compared to particles with an average particle size of a few nanometers (nm). Therefore, within this particle size range, the silica particles have excellent dispersion stability, allowing them to be uniformly distributed within the light-shielding film. Consequently, the reflectivity of the light-shielding film is less likely to vary.

Furthermore, the content of the silica particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, relative to the total mass of the photosensitive resin composition. When the silica particle content is within this range, low reflectivity can be achieved and good photopatterning properties can be ensured.

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

The silica particles may have a refractive index of 1.10 to 1.47. By using hollow silica particles with a low refractive index in addition to conventional silica particles with a refractive index of 1.45 to 1.47, the refractive index of the light-shielding film can be further reduced compared to the refractive index of a light-shielding film composed solely of conventional silica particles.

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

Furthermore, since reflection caused by the difference in refractive index between the transparent substrate and the formed light-shielding film can be suppressed, reflection can be suppressed even without separately providing an antireflection film or the like on the substrate.

The shape of the silicon dioxide particles can be spherical or elliptical. The shape of the silicon dioxide particles used in the present invention is preferably spherical.

The silica particles preferably have a sphericity of 1.0 to 1.5. When the sphericity of the silica particles is within this range, the particle shape is close to spherical. Therefore, the particles can be uniformly packed into thin light-shielding films, maintaining the film's surface smoothness while preventing the silica particles from protruding from the film surface. Consequently, a light-shielding film with a low refractive index and sufficient strength can be obtained.

The sphericity of the silica particles can be determined by taking the ratio of the longest to shortest diameters of the particles (average value for any 100 silica particles). The longest and shortest diameters of the silica particles are determined by measuring the longest and shortest diameters of the silica particles in the obtained microscopic images using a transmission electron microscope.

The silica particles (component (E)) can be mixed with the other ingredients as a silica particle dispersion dispersed in a solvent. Dispersants can be used without particular limitation, including known compounds used for dispersing pigments (light-shielding components) (commercially available compounds known as dispersants, dispersion wetting agents, dispersion accelerators, etc.). Furthermore, in this embodiment, the silica particle dispersion contains the dispersant (F) described below.

6. Component (F) The dispersant serving as component (F) in this embodiment has an acid value and an amine value, both of which are 10 mgKOH/g or higher and 80 mgKOH/g or lower. A dispersant with an amine value of 10 mgKOH/g or higher improves the dispersibility of silica particles. On the other hand, a dispersant with only an amine value improves the dispersibility of silica particles, but reduces their solubility in the developer, resulting in residue at the edges of the pattern and impaired linearity. In contrast, a dispersant with an amine value of 10 mgKOH/g or higher and an acid value of 10 mgKOH/g or higher improves the dispersibility of silica particles and enables the formation of high-definition patterns. On the other hand, by setting both the acid value and amine value to 80 mgKOH/g or less, the solubility of the silica particles protected by the dispersant in the developer solution is not excessively increased, thereby suppressing a decrease in the fineness of the formed pattern. From this perspective, the amine value and acid value of the dispersant are preferably both 30 mgKOH/g or more and 80 mgKOH/g or less, and more preferably both 30 mgKOH/g or more and 80 mgKOH/g or less.

This also improves the dispersibility of silica particles and suppresses the formation of aggregates derived from silica particles. Furthermore, the acid value of the dispersant (component (F)) refers to the number of milligrams of KOH required to neutralize 1 gram of the resin component (solid content) and can be measured in accordance with Japanese Industrial Standard (JIS)-K0070. The amine value of the dispersant (component (F)) refers to the number of milligrams of KOH equivalent to the amount of acid (such as acetic acid) required to neutralize 1 gram of the resin component (solid content) and can be measured in accordance with JIS-K7237.

Examples of dispersants as component (F) include alkylammonium salts and alkylolmmonium salts of acidic polymers, alkylammonium salts and alkylolmmonium salts of high molecular weight copolymers containing acidic groups, neutralized salts of polymers containing alkylamine groups, and phosphate salts of high molecular weight copolymers. Of these, alkylammonium salts of acidic polymers or high molecular weight copolymers containing acidic groups are preferred. Using alkylammonium salts and alkylolmmonium salts of acidic polymers or high molecular weight copolymers containing acidic groups as dispersants significantly suppresses the formation of aggregated foreign matter originating from silica particles.

Commercially available examples of the dispersant component (F) include DISPERBYK-140, 142, 145, 2001, 2025, and 9076 (all manufactured by BYK-Chemie Japan Co., Ltd.; "DISPERBYK" is a registered trademark of BYK-Chemie Japan Co., Ltd.). Of these commercially available products, DISPERBYK-140, 142, and 9076 are preferred, with DISPERBYK-140 and 9076 being more preferred.

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

Furthermore, the ratio (m _F /m _E ) of the total mass of the dispersant (F) (m _F ) to the total mass of the silica particles (E) (m _E ) is preferably 0.02 to 0.6, more preferably 0.03 to 0.4. When the ratio of the total mass of the dispersant (F) (m _F ) to the total mass of the silica particles (m _E ) is within this range, the reflectivity on the glass substrate side can be reduced, and the formation of aggregated foreign matter originating from the silica particles can be suppressed.

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

7. Solvent In the photosensitive resin composition of the present invention, it is preferred to use a solvent as component (G) in addition to components (A) to (F). Examples of solvents include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol and β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; solvents, methyl solvents, ethyl solvents, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol, and propylene glycol; Glycol ethers such as 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 acetates such as ethyl acetate, butyl acetate, solvent acetate, ethyl solvent acetate, butyl solvent acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. A uniform solution-like composition can be prepared by using these alone or in combination and dissolving and mixing two or more.

Furthermore, the photosensitive resin composition of the present invention may optionally contain additives such as resins other than component (A) such as epoxy resins, hardeners, hardening accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than silica, leveling agents, defoaming agents, surfactants, and coupling agents.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl o-cyclopentylphenol, phenothiazine, and hindered phenolic compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and aluminum oxide. Examples of defoamers and leveling agents include silicone, fluorine, and acrylic compounds. Examples of surfactants include fluorine-based and silicone-based surfactants. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

The photosensitive resin composition of the present invention preferably comprises, in a solid component excluding solvent (the solid component including monomers that solidify after photocuring), 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 a black pigment, a color-mixing pigment, and a light-shielding material as component (D), silica particles (E), and a dispersant (F). The amount of solvent varies depending on the target viscosity, but is preferably 40% to 90% by mass relative to the total weight.

The photosensitive resin composition of the present invention can be produced as a black anti-etching agent by mixing (A) an unsaturated group-containing photosensitive resin, (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. The silica particle dispersion (E) contains the dispersant (F).

By pre-incorporating the (F) dispersant into the (E) silica particle dispersion, the dispersion stability of the silica dispersion can be improved, and the formation of aggregated foreign matter can be prevented when mixing with other resin components.

A 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 curing the film by irradiating the film with light (including ultraviolet light, radiation, etc.). By using a mask or the like to separate the exposed and unexposed portions, curing only the exposed portions while dissolving the remaining portions with an alkaline solution, a desired pattern can be achieved.

In addition, a color filter or 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 with a thickness of 1.0 μm to 2.0 μm on a transparent substrate. After the light-shielding film is formed, red, blue, and green pixels are formed using photolithography; and red, blue, and green inks are injected into the light-shielding film using an inkjet process.

Furthermore, a light-shielding film formed by curing the photosensitive resin composition of the present invention can also be used as black columnar spacers in liquid crystal displays. For example, a single black resist can be used to create multiple sections with different film thicknesses, with one section functioning as a spacer and the other as a black matrix.

Each step of the method for forming a light-shielding film by coating and drying a photosensitive resin composition is specifically exemplified.

The photosensitive resin composition can be applied to the substrate using any of the known methods, including solution immersion, spraying, roll coaters, land coaters, slit coaters, or rotary coaters. After application to the desired thickness using these methods, the solvent is removed (pre-baked) to form a film. Pre-baking is performed by heating in an oven, hot plate, or vacuum drying, or a combination of these methods. The heating temperature and time during pre-baking are appropriately selected depending on the solvent used; for example, 80°C to 120°C for 1 to 10 minutes are preferred.

Radiation used for exposure can include, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. The wavelength range of the radiation is preferably 250 nm to 450 nm. In addition, suitable developer solutions for alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developers can be selected based on the properties of the resin layer, but the addition of a surfactant is also effective if necessary. The development temperature is preferably 20°C to 35°C, and a commercially available developer or ultrasonic cleaner can be used to precisely form a fine image. Alkaline development is typically followed by water washing. As a developing method, a spray developing method, a mist developing method, an immersion (dip) developing method, a puddle developing method, etc. can be applied.

After development, a heat treatment (post-bake) is performed at 180°C to 250°C for 20 to 100 minutes. This post-bake is performed to improve the adhesion between the patterned light-shielding film and the substrate. Similar to the pre-bake, this can be performed by heating in an oven, hot plate, or the like. The patterned light-shielding film of the present invention is formed through various steps based on photolithography. The heat then completes polymerization or curing (sometimes referred to collectively as curing), resulting in a light-shielding film with the desired pattern.

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

The photosensitive resin composition for black etch resist of the present invention is suitable for use as a coating material. In particular, it is useful as a color filter ink used in liquid crystal display devices or imaging elements, and a light-shielding film formed from such ink as a color filter or a black matrix for liquid crystal projectors. Furthermore, in addition to being used as a color filter ink for color liquid crystal displays, the photosensitive resin composition for black etch resist of the present invention can also be used as an ink material for color separation or light-shielding in various multicolor displays, such as organic electroluminescent (EL) devices, color liquid crystal displays, color facsimiles, and image sensors. The color filter of the present invention can reduce reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, or, when used in an organic EL device, reflection of the light emitted by the device. Specifically, by reducing reflection of external light, it is possible to improve contrast in bright areas, or by improving light extraction efficiency from the light-emitting side, thereby increasing luminous efficiency. [Examples]

Hereinafter, the embodiments of the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition, in the present invention, when the first decimal place is 0, the decimal place may be omitted.

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

[Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into 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 used to determine the solid content concentration using the following formula. Solid content concentration (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 using a gel permeation chromatography (GPC) instrument "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml/min). The weight-average molecular weight (Mw) was calculated using a standard polystyrene (PS-oligomer kit, manufactured by Tosoh Corporation).

[Average Particle Size] The average particle size of silica particles was determined using the dynamic light scattering method using the particle size analyzer "FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) and the cumulative method.

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows: BPFE: bisphenol fluorene epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxycyclopropane; in the compound of formula (1), X is fluorene-9,9-diyl and R ₁ to R ₄ are hydrogen) AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: tetrahydrophthalic anhydride TEAB: tetraethylammonium bromide PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were placed in a 500 ml four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 20 hours to react. BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were then added to the flask and stirred at 120°C to 125°C for 6 hours to obtain an alkali-soluble resin (A) containing unsaturated groups. The obtained resin solution had a solid content concentration of 56.0% by mass, an acid value (based on solid content) of 103 mgKOH/g, and an Mw of 3600 as determined by GPC analysis.

The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared using the amounts (in mass %) listed in Table 1. The ingredients used in Table 1 are as follows.

(Alkaline-soluble resin containing unsaturated groups) (A): Alkaline-soluble resin solution containing unsaturated groups obtained in the above synthesis example (solids concentration: 56.0 wt%)

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

(Photopolymerization Initiator) (C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (Irgacure OXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of BASF Japan) (C)-2: Adeka Arkls NCI-831, manufactured by ADEKA Co., Ltd., "Adeka Arkls" is a registered trademark of ADEKA Co., Ltd.)

(Carbon Black Dispersion) (D): Carbon black concentration: 25.0% by mass, polymer dispersant concentration: 2.0% by mass, PGMEA dispersion (solids: 35.0% by mass) in a dispersing resin (alkali-soluble resin (A) from the synthesis example (solids: 8.0% by mass)).

(E): PGMEA dispersion of silica particles "YA050C" (manufactured by Admatech Co., Ltd., solid content concentration: 30% by mass, average particle size: 50 nm)

(Dispersants) (F)-1: DISPERBYK-140 (52% solids by mass) (F)-2: DISPERBYK-142 (60% solids by mass) (F)-3: DISPERBYK-9076 (100% solids by mass) (F)-4: DISPERBYK-167 (52% solids by mass) (F)-5: DISPERBYK-170 (30% solids by mass) (F)-6: DISPERBYK-180 (solids content: 100% by mass) (F)-7: DISPERBYK-9077 (solids content: 100% by mass) (F)-1 through (F)-7 are manufactured by BYK-Chemie Japan. "DISPERBYK" is a registered trademark of BYK-Chemie Japan.

In addition, (F)-1 is a dispersant with an alkylammonium salt structure having an acidic polymer, (F)-2 is a phosphate ester type dispersant of a high molecular weight copolymer, (F)-3 is a dispersant with an alkylammonium salt structure containing a high molecular weight copolymer having an acidic group, (F)-4 is a urethane type dispersant, (F)-5 is a high molecular weight dispersant having an acidic functional group, (F)-6 is an ammonium alkoxide type dispersant of a copolymer containing an acidic group, and (F)-7 is a high molecular weight copolymer having an amine value.

(Solvent) (G)-1: Propylene glycol monomethyl ether acetate (PGMEA) (G)-2: Cyclohexanone (ANON)

[Table 1] Mixing ingredients Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 (A) 5.3 5.3 5.3 5.3 5.4 5.2 5.0 5.4 5.2 5.0 5.4 5.3 5.3 5.3 5.3 5.4 5.4 (B) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.7 1.6 1.6 1.6 1.6 1.7 1.7 (C) -1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (C) -2 0.3 (D) 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 (E) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (F) -1 0.11 0.06 0.35 0.58 0.01 (F) -2 0.10 (F) -3 0.06 0.06 0.03 0.18 0.30 0.006 (F) -4 0.11 (F) -5 0.20 (F) -6 0.06 (F) -7 0.06 (G) -1 28.0 28.0 28.0 28.0 27.9 27.8 27.8 28.0 28.0 28.1 27.9 28.0 27.9 28.0 28.0 27.9 27.9 (G) -2 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 38.7 Characteristic values of component F Acid value 73 46 38 38 73 73 73 38 38 38 - - 11 94 - 73 38 Amine value 76 43 44 44 76 76 76 44 44 44 - 13 - 94 48 76 44 m _E /m _D 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 _mF / _mE 0.10 0.10 0.10 0.10 0.05 0.30 0.50 0.05 0.30 0.50 - 0.10 0.10 0.10 0.10 0.01 0.01

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

(Production of a Light-Shielding Film for Evaluation) Using a rotary coater, the photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate "#1737" (Corning, Inc.) (hereinafter referred to as the "glass substrate"), which had been previously cleaned by irradiating the substrate with ultraviolet light at a wavelength of 254 nm and an illumination intensity of 1000 mJ/ ^cm² using a low-pressure mercury lamp. The film was then pre-baked at 90°C for 1 minute using a hot plate to produce a light-shielding film. Next, the exposure gap was adjusted to 100 μm, and a negative mask with a line/space ratio of 10 μm/50 μm was applied to the dry light-shielding film. Using an ultra-high-pressure mercury lamp with an i-ray and an illuminance of 30 mW/ ^cm2 , 50 mJ/ ^cm2 of ultraviolet light was applied to the photosensitive portion for a photohardening reaction.

Next, the exposed light-shielding film was developed at 25°C using a 0.04% potassium hydroxide solution at a spray pressure of 1 kgf/ ^cm2 for 10 seconds and 20 seconds from the development time (break time = BT) at which the pattern begins to appear. Thereafter, the film was washed with a 5 kgf/ ^cm2 spray water to remove the unexposed portion of the light-shielding film, thereby forming a light-shielding film pattern on the glass substrate. The film was then formally cured (post-baked) at 230°C for 30 minutes in a hot air dryer to obtain light-shielding films for evaluation of Examples 1 to 10 and Comparative Examples 1 to 7.

The produced light-shielding films for evaluation were evaluated on the following items.

[Pattern Linearity Evaluation] (Evaluation Method) After the main curing (post-baking), the 10 μm mask pattern was observed using an optical microscope and a scanning electron microscope (SEM) to detect jagged edges. Pattern linearity was evaluated at both a BT+10 second and a BT+20 second cycle. A score of 0 or higher was considered acceptable.

(Evaluation Criteria) ○: No jagged edges observed △: Jagged edges observed partially X: Jagged edges observed throughout the entire pattern

[Optical Density Evaluation] (Evaluation Method) The optical density (OD) of the prepared light-shielding film for evaluation was determined using a Macbeth density meter. The thickness of the light-shielding film formed on the substrate was also measured, and the value obtained by dividing the optical density (OD) by the film thickness was defined as OD/μm.

Optical density (OD) is calculated using the following formula (1). Optical density (OD) = -log ₁₀ T (1) (T represents transmittance)

[Reflectivity Evaluation] (Evaluation Method) For a substrate with a light-shielding film, prepared similarly to the light-shielding film used for evaluation, the reflectivity of the substrate (glass substrate) side was measured at an incident angle of 2° using a UV-Vis-Infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science, Ltd.). A score of △ or higher was considered acceptable. (Evaluation Criteria) ○: The reflectivity of the substrate side of the substrate with the light-shielding film was 5% or less. △: The reflectivity of the substrate side of the substrate with the light-shielding film exceeded 5% and was less than 6%. X: The reflectivity of the substrate side of the substrate with the light-shielding film was 6% or higher.

[Agglomerated Foreign Matter Evaluation] (Evaluation Method) After the final curing (post-baking), the evaluation light-shielding film was inspected using an optical microscope to check for the presence of aggregated foreign matter. A score of △ or higher was considered acceptable.

(Evaluation Criteria) ○: No aggregated foreign matter was observed on the light-shielding film △: Aggregated foreign matter was observed on a portion of the light-shielding film X: Aggregated foreign matter was observed on the entire surface of the light-shielding film

The evaluation results are shown in Table 2.

[Table 2] Mixing ingredients Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 Optical density (OD) 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 Reflectivity/substrate side (%) 4.8 (0) 4.8 (0) 4.9 (0) 4.9 (0) 4.8 (0) 4.9 (0) 5.5 (△) 4.8 (0) 5.0 (0) 5.6 (△) 4.8 (0) 4.8 (0) 4.8 (0) 4.8 (0) 4.8 (0) 4.8 (0) 4.9 (0) Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ △ △ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ × × ○ ○ Condensed foreign matter evaluation ○ △ ○ ○ ○ ○ ○ ○ ○ ○ × △ × ○ ○ × ×

As shown in Examples 1 to 10, it was found that using a dispersant with an acid value and an amine value of 10 mgKOH/g or higher and 80 mgKOH/g or lower allowed for the formation of high-definition patterns. On the other hand, when both the acid value and the amine value exceeded 80 mgKOH/g, the solubility in the developer solution became excessively high, resulting in a deterioration in the linearity of the pattern.

Furthermore, as shown in Examples 1 to 10, the jagged edges of the patterns were eliminated compared to Comparative Examples 2 and 5, which used dispersants with only an amine value. This is believed to be because adsorption of the dispersant onto the silica particles tends to reduce their solubility in the developer solution, whereas the use of a dispersant with both an acid value and an amine value ensures the solubility of the silica particles in the developer solution.

Furthermore, as shown in Examples 1 to 10, the use of a dispersant having an acid value and an amine value of 10 mgKOH/g or higher and 80 mgKOH/g or lower improves the dispersion stability of silica particles and suppresses the formation of aggregated foreign matter. In particular, Examples 1 and 3 to 10, which utilize polymeric dispersants having an alkylammonium salt structure, significantly suppress the formation of aggregated foreign matter originating from silica particles. This is believed to be due to the effective protection of the silanol groups present on the surface of the silica particles by the dispersant, thereby improving the dispersion stability of the silica particles in the photosensitive composition for black resist.

As shown in Examples 1 to 10, it was found that by setting the ratio (m _F /m _E ) of the total mass of the (F) dispersant (m _F ) to the total mass of the (E) silica particles (m _E ) to 0.02 to 0.6, the reflectance on the glass substrate side can be suppressed to 5% or less, and the formation of aggregates originating from the silica particles can be suppressed. If m _F /m _E is below this range, the dispersion stability of the silica particles is insufficient, resulting in the formation of aggregates. On the other hand, if m _F /m _E is above this range, the compatibility of the silica particles becomes excessively high, and the reflectance on the glass substrate side exceeds 5% due to the lack of localization near the glass substrate. [Industrial Applicability]

The photosensitive resin composition of the present invention provides a black matrix photosensitive resin composition with both high light-shielding properties and low reflectivity, as well as a light-shielding film, color filter, and touch panel using the same. Furthermore, the color filter and touch panel can be used to provide various display devices with excellent visibility.

without

Claims (10)

A photosensitive resin composition for a black resist comprises: (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 color-mixing pigment, and a light-shielding material; (E) silica particles; and (F) a dispersant, wherein the dispersant (F) has an acid value and an amine value, each of which is not less than 10 mgKOH/g and not more than 80 mgKOH/g, and a ratio ( _mF / _mE ) of the total mass ( _mF ) of the dispersant (F) to the total mass ( _mE ) of the silica particles (E) is 0.03 to 0.40. The photosensitive resin composition for black anti-etching agent according to claim 1, wherein the photosensitive resin (A) containing an unsaturated group is a photosensitive resin containing an unsaturated group obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from a diphenol represented by the following general formula (1) with (meth)acrylic acid, and further reacting the reaction product with a polycarboxylic acid or an anhydride thereof, (In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom; 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 anti-etching agent according to claim 1 or claim 2, wherein the dispersant (F) is a polymer compound having an alkylammonium salt structure. The photosensitive resin composition for black anti-etching agent according to claim 1 or claim 2, wherein the average particle size of the silica particles (E) is 1 nm to 100 nm. The photosensitive resin composition for a black anti-etching agent according to claim 1 or claim 2, wherein the ratio (m E /m _D ) of the total mass (m _E ) of the (E) silica particles to the total mass (m _D ) of the (D) _light -shielding component is 0.01 to 0.20. A method for producing a photosensitive resin composition for a 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 obtained by dispersing a light-shielding component in a solvent, and (E) a silica particle dispersion obtained by dispersing silica particles in a solvent, wherein the silica particle dispersion (E) contains (F) a dispersant having an acid value and an amine value, both of which are 10 mgKOH/g or more and 80 mgKOH/g or less, and a ratio (m _F /m _E) of the total mass (m _F ) of the dispersant (F) to the total mass (m _E ) of the silica particles (E) ) is 0.03~0.40. A light-shielding film is formed by curing the photosensitive resin composition for black anti-etching agent as described in any one of claims 1 to 5. A color filter having the light-shielding film according to claim 7 as a black matrix. A touch panel having the light-shielding film according to claim 7 as a black matrix. A display device having the color filter according to claim 8 or the touch panel according to claim 9.