TW202202531A - Photosensitive resin composition for black resist, method for producing the same, light-shielding film, color filter, touch panel, and display device Capable of forming a high-definition pattern, and can suppress the generation of aggregated foreign matter - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a black resist which has high light-shielding properties and low reflectance, can form a high-definition pattern, and can suppress the generation of aggregated foreign matter. The photosensitive resin composition for black resists of the present invention includes (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, and (C) A photopolymerization initiator, (D) at least one light-shielding component selected from the group consisting of black pigments, color mixing pigments, and light-shielding materials, (E) silica particles, and (F) a dispersant. The (F) dispersing agent has an acid value and an amine value, the acid value and the amine value are both 10 mgKOH/g or more and 80 mgKOH/g or less, and the total mass (mF) of the (F) dispersing agent The ratio (mF/mE) to the total mass (mE) of the (E) silica particles is 0.02 to 0.60.

Description

Photosensitive resin composition for black resist, method for producing the same, 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 obtained by curing the photosensitive resin composition for a black resist, and a light-shielding film having the light-shielding film. A color filter and a touch panel of a film, and a display device having the color filter and the touch panel.

In recent years, with the development of mobile terminals, display devices such as touch panels and liquid crystal panels used for outdoor or in-vehicle applications have increased. In the display device, a light-shielding film is arranged on the outer frame of the touch panel to shield the light leakage of the peripheral portion of the liquid crystal panel on the back side, and a black matrix is arranged on the liquid crystal panel to suppress the leakage of light from the screen during black display and to suppress the adjacent ones. color resists are mixed with each other.

In a display device or the like, in order to suppress light leakage or the like and improve the visibility of the screen of the display device or the like, the concentration of the black pigment in the light-shielding film may be increased to improve the light-shielding property of the light-shielding film (reduce the light-transmitting property of the light-shielding film). . Since the refractive index of the black pigment is higher than the refractive index of the transparent substrate or the curable resin, if the concentration of the black pigment in the light-shielding film is increased, the surface of the transparent base material opposite to the surface on which the light-shielding film is formed is increased. When observing, the reflectance becomes high. Therefore, reflection at the interface between the light-shielding film formed on the transparent base material and the transparent base material increases, and reflection on the light-shielding film or a black matrix boundary due to the difference in reflectance from the colored portion of the color filter occurs. Conspicuous bad condition.

Therefore, the photosensitive resin composition for black resists which have both high light-shielding property and low reflectance, and the light-shielding film and color filter which hardened it are eagerly desired.

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

[Patent Document 1] Japanese Patent Laid-Open No. 2015-161815

[Problems to be Solved by Invention] However, the inventors of the present invention have conducted studies, and as a result, the black photosensitive resin composition described in Patent Document 1 has the following problems: during pattern formation, the pattern edge portion is zigzag, or a source is generated on the black matrix. Agglomerated foreign matter from silica particles.

The present invention has been made in view of the above-mentioned aspects, and an object of the present invention is to provide a photosensitive resin composition for a black resist which has high light-shielding properties and low reflectance, can form a high-definition pattern, and can suppress the generation of aggregated foreign matter, and A light-shielding film formed by curing, a color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel. [Technical means to solve the problem]

The photosensitive resin composition for black resists of the present invention contains: (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, and (C) a light A polymerization initiator, (D) at least one light-shielding component selected from the group consisting of black pigments, color mixing pigments, and light-shielding materials, (E) silica particles, and (F) a dispersant, the (F) The dispersant has an acid value and an amine value, the acid value and the amine value are both 10 mgKOH/g or more and 80 mgKOH/g or less, and the total mass (m _F ) of the (F) dispersant is relative to the (E) The ratio (m _F /m _E ) of the total mass (m _E ) of the silica particles is 0.02 to 0.60.

The method for producing the photosensitive resin composition for a black resist of the present invention is to mix (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and ( 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 are mixed, and the photosensitive resin for the black resist is mixed In the manufacturing method of the composition, the (E) silica particle dispersion contains (F) a dispersant, and the (F) dispersant has an acid value and an amine value, and the acid value and the amine value are both. 10 mgKOH/g or more and 80 _mgKOH /g or less, the ratio (m _{F /} m _E ) is 0.02 to 0.60.

The light-shielding film of this invention hardens the said photosensitive resin composition for black resists.

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. [Effect of invention]

According to the present invention, there can be provided a photosensitive resin composition for a black resist, which has high light-shielding properties and low reflectance, can form a high-definition pattern, and can suppress the generation of agglomerated foreign matter, and a light-shielding film obtained by curing the same, A color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel.

Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resists of the present invention (hereinafter, simply referred to as "photosensitive resin composition") includes (A) a photosensitive resin containing an unsaturated group, and (B) a photosensitive resin having at least two or more unsaturated groups. Bonded photopolymerizable monomer, (C) photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, color mixing pigments, and light-shielding materials, (E) silica particles, and (F) dispersion agent. Hereinafter, (A) component - (F) component are demonstrated.

1. (A) Ingredient The unsaturated group-containing photosensitive resin as the component (A) of the present embodiment preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably contains a polymerizable unsaturated group. Both saturated and carboxyl groups. It does not specifically limit as long as it is the said resin, It can use widely.

Examples of the unsaturated group-containing photosensitive resin include epoxy (meth)acrylate acid adducts obtained by combining (meth)acrylic acid with a bisphenol-derived glycidol having two glycidols. An ether-based epoxy compound (hereinafter, also referred to as "bisphenol-type epoxy compound represented by the general formula (1)") reacts to obtain a compound having a hydroxyl group, and a polyvalent carboxylic acid or an anhydride thereof is reacted with the obtained compound having a hydroxyl group. Hydroxyl compounds react. The epoxy compound derived from bisphenols refers to an epoxy compound obtained by reacting bisphenols with an epihalohydrin or an equivalent thereof. In addition, "(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 the component (A) is preferably a bisphenol-type epoxy compound represented by the following general formula (1).

[hua 1]

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9 represented by the general formula (2), 9-diradical or single bond, l is an integer from 0 to 10)

[hua 2]

The bisphenol-type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. At the time of the said reaction, oligomerization of a diglycidyl ether compound is usually accompanied, and therefore, an epoxy compound containing two or more bisphenol skeletons is included.

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) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5-dichlorobenzene) 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-dimethysilane) Chlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl) ) methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3 ,5-Dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxy-3-chlorophenyl)propane -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 preferable.

Moreover, the example of the acid monoanhydride of (a) dicarboxylic acid or tricarboxylic acid reacted with the hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid It includes: acid monoanhydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid, acid monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid, acid monoanhydride of aromatic dicarboxylic acid or tricarboxylic acid, and the like. Here, examples of the acid monoanhydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, Acid monoanhydrides of malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Furthermore, the acid monoanhydride of dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced, etc. are included. In addition, examples of the acid monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane Acid monoanhydrides such as alkanedicarboxylic acids. Furthermore, the acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced, and the like are also included. In addition, examples of the acid monoanhydride of an aromatic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as phthalic acid, isophthalic acid, and trimellitic acid. Furthermore, it contains the acid monoanhydride of the dicarboxylic acid or tricarboxylic acid which introduce|transduced arbitrary substituents.

Moreover, as the acid dianhydride of (b) tetracarboxylic acid which reacts with epoxy (meth)acrylate, the acid dianhydride of chain hydrocarbon tetracarboxylic acid, the acid dianhydride of alicyclic tetracarboxylic acid, or the acid dianhydride of alicyclic tetracarboxylic acid can be used. Acid dianhydrides of aromatic tetracarboxylic acids. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Furthermore, the acid dianhydride of tetracarboxylic acid etc. which introduce|transduce arbitrary substituents are contained. In addition, examples of the acid dianhydride of alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid and other acid dianhydrides. Furthermore, the acid dianhydride of tetracarboxylic acid etc. which introduce|transduce arbitrary substituents are contained. In addition, examples of the acid dianhydride of the aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid. Furthermore, the acid dianhydride of tetracarboxylic acid etc. which introduce|transduce arbitrary substituents are contained.

The molar ratio (a)/(b) of (a) acid monoanhydride of dicarboxylic acid or tricarboxylic acid and (b) acid dianhydride of tetracarboxylic acid to be reacted with 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) deviates from the above range, the optimum molecular weight for making the photosensitive resin composition having favorable photopatternability cannot be obtained, which is not preferable. Furthermore, there is a tendency that the smaller the molar ratio (a)/(b), the larger the molecular weight and the lower the alkali solubility.

Moreover, the reaction of an epoxy compound and (meth)acrylic acid, and the reaction of the epoxy (meth)acrylate obtained by the said reaction, and polyhydric carboxylic acid or its acid anhydride are not specifically limited, A well-known method can be employ|adopted. In addition, the weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin synthesized by the reaction is preferably 2,000 to 10,000, and the acid value is preferably 30 mgKOH/g to 200 mgKOH/g. The acid value can be obtained by dissolving the resin solution in dioxane, for example, by using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) and titrating it with a 1/10 N-KOH aqueous solution. ask for. In addition, the weight-average molecular weight (Mw) of the unsaturated group-containing photosensitive resin can be, for example, using a gel permeation chromatography (Gel Permeation Chromatograph, GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd.) to measure.

Regarding the unsaturated group-containing photosensitive resin as the component (A), other examples of preferable resins include copolymers such as (meth)acrylic acid, (meth)acrylate, and the like, and having (meth)acryloyl hydride and carboxyl-based resins. Examples of the resin include polymerizable unsaturated group-containing alkali-soluble resins obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, And (meth)acrylic acid is made to react with the obtained copolymer, and finally the anhydride of dicarboxylic acid or tricarboxylic acid is made to react. For the copolymer, reference can be made to: 20 mol% of repeating units derived from diester glycerol obtained by esterifying hydroxyl groups at both ends with (meth)acrylic acid, as described in Japanese Patent Laid-Open No. 2014-111722 10 mol% to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 mgKOH /g to 120 mgKOH/g; and, as shown in Japanese Patent Laid-Open No. 2018-141968, comprising a unit derived from a (meth)acrylate compound, and a (meth)acryloyl group and a A polymer having a unit of carboxylic acid residue or tricarboxylic acid residue, a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 mgKOH/g to 200 mgKOH/g is an alkali-soluble polymer containing a polymerizable unsaturated group. resin.

About the unsaturated-group containing photosensitive resin of (A) component, only 1 type may be used independently, and 2 or more types may be used together.

2. (B) Ingredient Examples of the photopolymerizable monomer having at least two or more unsaturated bonds as the component (B) of the present embodiment include ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylic acid Esters, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, triglyceride Methylol propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Acrylates, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. (methyl) acrylic acid esters, dendrimer having a (meth)acryloyl group as a compound having an ethylenic double bond, and the like. Only one kind of these monomers may be used alone, or two or more kinds may be used in combination. In addition, the photopolymerizable monomer having at least two ethylenically unsaturated bonds functions to crosslink the molecules of the alkali-soluble resin contained in the photopolymerizable monomer. substances with saturated bonds. In addition, the acrylic acid equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acrylic groups in one molecule is preferably 50 to 300, and the acrylic equivalent is more preferably 80 to 200. In addition, (B) component does not have a free carboxyl group.

As an example of a dendrimer having a (meth)acryloyl group as a compound having an unsaturated bond which can be contained in the composition as the component (B), (meth)acrylate (meth)acrylate A dendrimer obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bond in the meth)acryloyl group. Specifically, it is obtained by reacting the (meth)acryloyl group of the polyfunctional (meth)acrylate represented by the following general formula (3) with the polyvalent mercapto compound represented by the following general formula (4). dendrimers, etc.

[hua 3]

(In formula (3), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the residue after donating n hydroxyl groups out of k hydroxyl groups of R ₇ (OH) _k 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 plurality of molecules of the polyol are dehydrated and condensed through an alcohol and via an ether Polyol ethers that are linked by bonds, or esters of these polyols or polyol ethers and hydroxy acids; k and n independently represent an integer of 2 to 20, k≧n)

[hua 4]

(In formula (4), R ₈ is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, m is 2 when R ₈ is a single bond, and when R ₈ is a divalent to hexavalent group Same valence as R ₈ )

Examples of the polyfunctional (meth)acrylate represented by the general formula (3) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (Meth)acrylates such as acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, etc. Only one of these compounds may be used alone, or two or more of them may be used in combination.

Examples of the polyvalent mercapto compound represented by the general formula (4) include trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), Pentaerythritol tris(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. Only one of these compounds may be used alone, or two or more of them may be used in combination.

The compounding ratio of (A) component and (B) component is a weight ratio (A)/(B), Preferably it is 30/70 - 90/10, More preferably, it is 60/40 - 80/20. If the blending ratio of the component (A) is 30/70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film at the unexposed portion is less likely to be lowered, so that the acid value of the coating film with respect to the alkaline developer can be suppressed. Decreased solubility. Therefore, it is difficult to cause problems such as zigzag pattern edges or indistinctness. Moreover, since the ratio of the photoreactive functional group in resin is sufficient as the compounding ratio of (A) component is 90/10 or less, formation of a desired crosslinked structure can be performed. In addition, since the acid value of the resin component does not become too high, the solubility of the exposed portion with respect to the alkaline developing solution is not likely to increase, so that the formed pattern can be prevented from becoming thinner than the target line width or the loss of the pattern. .

3. (C) Ingredient Examples of the photopolymerization initiator as (C) component of the present embodiment include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminobenzene Acetophenones such as acetone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamine Benzophenones such as benzophenone; benzoin ethers such as benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, 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-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-styrene base-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-( halomethylthiazole compounds such as p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine oxazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis (Trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3, Halogenated methyl-s-triazine compounds such as 5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyl oxime ), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane- 1,2-Dione-2-oxime-O-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 and other O-acyl oxime compounds; benzyl dimethyl ketal, sulfur Sulfur compounds such as xanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethyl Anthraquinones such as anthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzyl peroxide, cumene peroxide Organic peroxides such as oxides; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; tertiary compounds such as triethanolamine and triethylamine Amines etc. Only one of these photopolymerization initiators may be used alone, or two or more of them may be used in combination.

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

[hua 5]

(In formula (5), R ₉ and R ₁₀ each 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 an arylalkyl group having 4 to 12 carbon atoms. , R ₁₁ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms; ～10 alkyl groups, 1-10 carbon alkoxy groups, 1-10 carbon alkanoyl groups, halogen-substituted, alkylene moieties may contain unsaturated bonds, ether bonds, thioether bonds, ester bonds; in addition , the alkyl group can be any one of straight chain, branched, or cyclic)

[hua 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 having 4 to 10 carbon atoms, a cycloalkylalkyl group, or Alkylcycloalkyl, or a phenyl group that 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, the A part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted with an -O- group; further, a part of the hydrogen atoms in the groups of these R ₁₂ to R ₁₄ may also be substituted with a halogen atom)

The usage-amount of the photopolymerization initiator of the (C) component is preferably 3 parts by weight or more and 30 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of the total of each component of the (A) component and the (B) component. Part by weight or more and less than or equal to 20 parts by weight. When the blending ratio of the component (C) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be obtained. When the compounding ratio of (C) component is 30 weight part or less, since it can have moderate sensitivity, a desired pattern line width and a desired pattern edge can be obtained.

4. (D) Ingredient Light-shielding components such as black pigments, color-mixing organic pigments, and light-shielding materials, which are components (D) of the present embodiment, have an average particle diameter of 1 nm to 1000 nm (using a laser diffraction/scattering method particle size distribution meter or dynamic light A known light-shielding component can be used without particular limitation as the component dispersed in the average particle diameter measured by the particle size distribution meter by the scattering method.

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

Examples of color-mixing organic pigments as the component (D) include: azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindole pigments At least two-color mixing of organic pigments such as linoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments made of pigments.

According to the function of the target photosensitive resin composition, only one of the components (D) may be used alone, or two or more of them may be used in combination.

In addition, the example of the organic pigment which can be used when using a color mixing organic pigment as (D)component includes the pigment of the following number in the name of a dye index (Color Index), but it is not limited to this. Pigment red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment green 7, 36, 58, etc. Pigment blue (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-shielding component of the component (D) can be arbitrarily determined according to the desired light-shielding degree, but is preferably 20% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 80% by mass or less with respect to the solid content in the photosensitive resin composition 40 mass % or more and 70 mass % or less. Regarding the light-shielding component of the component (D), in the case of using organic pigments such as aniline black, cyanine black, and lactamide black, or carbon-based light-shielding components such as carbon black, it is particularly preferable to be relative to the solids in the photosensitive resin composition. It is 40 mass % or more and 60 mass % or less as a component. When the light-shielding component is 20 mass % or more with respect to the solid content in the photosensitive resin composition, light-shielding properties can be sufficiently obtained. If the light-shielding component is 80 mass % or less with respect to the solid content in the photosensitive resin composition, the content of the photosensitive resin originally serving as a binder does not decrease, so desired developing characteristics and film forming ability can be obtained.

The component (D) is usually mixed with other formulation components in the form of a light-shielding component dispersion dispersed in a solvent, and in this case, a dispersant may be added. As the dispersant, well-known compounds (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) and the like used for dispersion of pigments (light-shielding components) can be used without particular limitation.

Examples of dispersants include cationic polymer-based dispersants, anionic polymer-based dispersants, nonionic polymer-based dispersants, and pigment derivative-type dispersants (dispersing aids). In particular, the dispersant preferably has a cationic functional group such as an imidazole group, a pyrrole group, a pyridyl group, a primary amino group, a secondary amino group, or a tertiary amino group, and an amine value in terms of adsorption of colorants. It is a cationic polymer-based dispersant having a number average molecular weight (Mn) of 1 mgKOH/g to 100 mgKOH/g and a range of 1,000 to 100,000. It is preferable that the compounding quantity of the said dispersing agent is 1 mass % - 35 mass % with respect to a light-shielding component, and it is more preferable that it is 2 mass % - 25 mass %. In addition, resin-like high-viscosity substances generally have the effect of stabilizing dispersion, but substances that do not have dispersion-promoting ability are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

In addition, the ratio (m _E /m _D ) of the total mass (m _E ) of the (E) silica particles (described later) to the total mass (m _D ) of the (D) light-shielding component is preferably 0.01 to 0.20, More preferably, it is 0.05-0.1. If 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 in the above-described range, both high light-shielding properties and low reflectance can be achieved.

5. (E) Ingredient Regarding the silica particles as the component (E), there are no particular limitations on the production method such as gas phase reaction or liquid phase reaction, or the shape (spherical, non-spherical).

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

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

The average particle diameter of the silica particles is preferably 1 nm to 100 nm, and more preferably 10 nm to 90 nm. Compared with the case where the average particle diameter is a small particle diameter such as several nanometers (nm), it is considered that the aggregation of the silica particles is less likely to occur when the particle diameter is within the above-mentioned range. As a result, within the range of the particle diameter, the silica particles are excellent in dispersion stability, and thus can be uniformly present in the light-shielding film. Therefore, the reflectance on the light-shielding film is less likely to vary.

Moreover, 0.1 mass part - 5 mass parts are preferable with respect to the total mass of the photosensitive resin composition, and, as for content of the said silica particle, 0.1 mass part - 2 mass parts are more preferable. When the content of the silica particles is within the above-mentioned range, the reflectance can be lowered and favorable photopatternability can be ensured.

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

In addition, as the silica particles, particles having a refractive index of 1.10 to 1.47 can be used. By using hollow silica particles having a low refractive index in addition to ordinary silica particles having a refractive index of 1.45 to 1.47, the refractive index of a light-shielding film containing only ordinary silica particles can be reduced. In other words, the refractive index of the light-shielding film can be further reduced.

In addition, the refractive index of the silica particles can be obtained from a transparent mixed solution obtained by processing the silica particles into a powder form and a standard refractive solution of which the refractive index is known. obtained by mixing. 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 said silica particle can be measured using an Abbe refractometer.

In addition, since the reflection due to the difference in refractive index between the transparent base material and the formed light-shielding film can be suppressed, even if an antireflection film or the like is not separately provided on the base material, the reflection can be suppressed.

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

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

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

The silica particles as the component (E) can be mixed with other preparation components as a silica particle dispersion dispersed in a solvent. As the dispersing agent, known compounds (compounds marketed under the names of dispersing agents, dispersion wetting agents, dispersion accelerators, etc.) and the like which are used for dispersion of pigments (light-shielding components) and the like can be used without particular limitation. In addition, in this embodiment, the said silica particle dispersion contains the (F) dispersing agent mentioned later.

6. (F) Ingredients The dispersing agent which is (F) component of this embodiment has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH/g or more and 80 mgKOH/g or less. When the amine value of the dispersant is 10 mgKOH/g or more, the dispersibility of the silica particles can be improved. On the other hand, a dispersant having only an amine value improves the dispersibility of the silica particles, but reduces the solubility of the silica particles in the developing solution, so it remains as a residue on the edge of the pattern, and the linearity is reduced. reduce. On the other hand, when the amine value of the dispersant is 10 mgKOH/g or more and the acid value is also 10 mgKOH/g or more, the dispersibility of the silica particles can be improved, and a high-definition pattern can be formed. On the other hand, by setting both the acid value and the amine value to be 80 mgKOH/g or less, the solubility of the silica particles protected by the dispersing agent in the developer solution is not excessively increased, and the resulting pattern can be suppressed from being damaged. Decreased refinement. From this viewpoint, the amine value and the acid value of the dispersant are preferably both 30 mgKOH/g or more and 80 mgKOH/g or less, and more preferably both are 30 mgKOH/g or more and 80 mgKOH/g or less.

In addition, the dispersibility of the silica particles can be improved, and the generation of agglomerated foreign matter derived from the silica particles can be suppressed. In addition, the acid value of the dispersing agent as the component (F) refers to the number of mg of KOH required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with Japanese Industrial Standard (JIS)-K0070 . The amine value of the dispersing agent as the component (F) refers to the number of mg of KOH in equivalents with respect to the amount of acid (acetic acid, etc.) required to neutralize 1 g of the resin component (solid content), and can be based on JIS-K7237 to measure.

Examples of the dispersing agent as the component (F) include alkylammonium salts and alkanolammonium salts of acidic polymers, or alkylammonium salts and alkanolammonium salts of polymer copolymers having acid groups Salts, neutralized salts of polymers having alkylamine groups, phosphate ester salts of polymer copolymers, and the like. Among these, an alkylammonium salt of an acidic polymer or an alkylammonium salt of a polymer copolymer having an acid group is preferable. By using an alkylammonium salt or an alkanolammonium salt of an acidic polymer, or an alkylammonium salt or an alkanolammonium salt of a polymer copolymer having an acid group as a dispersant, it is possible to suppress the silica particles more significantly the production of agglomerated foreign bodies.

In addition, examples of commercially available products as dispersants of the component (F) include: DISPERBYK-140, 142, 145, 2001, 2025, 9076 (all BYK-Chemie Japan ) company, "DISPERBYK" is a registered trademark of BYK-Chemie Japan) and so on. Among the commercial products, DISPERBYK-140, 142, and 9076 are preferable, and DISPERBYK-140 and 9076 are more preferable.

(F) It is preferable that content of a dispersing agent is 0.01 mass part - 0.5 mass part with respect to the total mass of the photosensitive resin composition.

In addition, 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 preferably 0.02 to 0.6, more Preferably it is 0.03-0.4. If the ratio of the total mass (m _F ) of the (F) dispersing agent to the total mass (m _E ) of the silica particles is in the above range, the reflectance on the glass substrate side can be reduced, and the reflectance from the glass substrate side can be suppressed. Generation of agglomerated foreign matter of silica particles.

The dispersion liquid used for the photosensitive resin composition of this invention can be prepared by mixing and dispersing the said (A) component - (F) component by an appropriate method.

7. Solvents In the photosensitive resin composition of this invention, it is preferable to use the solvent which is (G) component in addition to (A) component - (F) component. Examples of solvents include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol or β-terpineol; acetone, methyl ethyl ketone, Cyclohexanone, N-methyl-2-pyrrolidone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol , methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol ethers such as alcohol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol Acetates such as bisphenol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By using these alone or in combination of two or more, dissolving and mixing, a uniform solution-like composition can be obtained.

In the photosensitive resin composition of the present invention, resins other than the component (A) such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, and other substances other than silicon dioxide may be blended as necessary. Filler, leveling agent, defoamer, surfactant, coupling agent and other additives.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like. Examples of the plasticizer include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of filler materials include: fiberglass, silica, mica, alumina, and the like. Examples of the defoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include: 3-(glycidyloxy)propyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Ureidopropyltriethoxysilane, etc.

The photosensitive resin composition of the present invention preferably contains the unsaturated group-containing photosensitive resin as the component (A) in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after photocuring), and as the The photopolymerizable monomer having at least two or more unsaturated bonds as the component (B), the photopolymerization initiator as the component (C), and the component (D) selected from black pigments, color mixing pigments, and light-shielding materials of at least one light-shielding ingredient, (E) silica particles, and (F) a dispersant. The amount of the solvent varies depending on the target viscosity, but is preferably 40% by mass to 90% by mass relative to the entire amount.

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

By preliminarily containing the (F) dispersant in the (E) silica particle dispersion, the dispersion stability of the silica dispersion can be improved, and the generation of agglomerated foreign matter can be prevented when mixing with other resin components.

In addition, the light-shielding film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition on a substrate or the like, drying the solvent, and irradiating light (including ultraviolet rays, radiation, etc.) to harden it. A desired pattern can be obtained by providing a portion irradiated with light and a portion not irradiated with light using a photomask or the like, hardening only the portion irradiated with light, and dissolving the other portion with an alkaline solution.

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

In addition, the light-shielding film which hardened the photosensitive resin composition of this invention can also be used as a black columnar spacer of a liquid crystal display device. For example, a plurality of portions with different film thicknesses may be formed using a single black resist, and one may function as a spacer and the other may function as a black matrix.

Each step of the film-forming method of the light-shielding film by coating/drying of the photosensitive resin composition will be specifically exemplified.

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

As radiation used for exposure, for example, visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, etc. can be used, and the wavelength range of the radiation is preferably 250 nm to 450 nm. Moreover, as a developing solution suitable for the said alkali image development, the aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used, for example. These developing solutions can be appropriately selected according to the properties of the resin layer, but it is also effective to add a surfactant as needed. The developing temperature is preferably 20° C. to 35° C., and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, or the like. In addition, water washing is usually performed after alkali development. As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied.

After developing in this way, heat treatment (post-baking) is performed at 180° C. to 250° C. for 20 minutes to 100 minutes. The post-baking is performed for the purpose of improving the adhesiveness between the patterned light-shielding film and the substrate, and the like. It can be performed by heating with an oven, a hotplate, etc. similarly to prebaking. The patterned light-shielding film of the present invention is formed through various steps based on a photolithography method. Furthermore, the light-shielding film which has a desired pattern can be obtained by completion|finishing superposition|polymerization or hardening (it may be called hardening together) by heat.

As described above, the photosensitive resin composition for a black resist of the present invention is not only suitable for forming fine patterns by operations such as exposure and alkali development, but also can obtain light-shielding properties in the same manner even when patterns are formed by conventional screen printing. , Adhesion, electrical insulation, heat resistance, chemical resistance excellent light-shielding film.

The photosensitive resin composition for black resists of this invention can be used suitably as a coating material. In particular, inks for color filters used in liquid crystal display devices and imaging elements, and light-shielding films formed of the inks are useful as color filters, black matrices for liquid crystal projection, and the like. In addition, the photosensitive resin composition for a black resist of the present invention can be used not only as a color filter ink for a color liquid crystal display, but also as an organic electroluminescence device represented by an organic electroluminescence (EL) element. , Color liquid crystal display devices, color facsimile machines, image sensors and other multi-color display materials for color division or shading ink materials. According to the color filter of the present invention, reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, or reflection of light emitted from the element when used in an organic EL element, for example, can be reduced. That is, it is possible to improve the contrast at bright spots by reducing the reflection of external light, or to improve the luminous efficiency by improving the light extraction efficiency from the light emitting side. [Example]

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition, in this invention, regarding the content of each component, when the 1st decimal place is 0, the expression after a decimal point may be abbreviate|omitted.

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

[Solid Content Concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160° C. for 2 hours according to The resulting weight [W ₂ (g)] was obtained by the following formula. Solid content concentration (% by weight)=100×(W ₂ -W ₀ )/(W ₁ -W ₀ )

[acid value] The resin solution was dissolved in dioxane, and a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) was used to titrate it with a 1/10 N-KOH aqueous solution to obtain it.

[Molecular weight] Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + 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) were measured and used as The weight average molecular weight (Mw) was calculated|required by the conversion value of standard polystyrene (Tosoh Co., Ltd. product, PS-oligomer set).

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

Abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: bisphenol fluorene type epoxy compound (the reaction product of 9,9-bis(4-hydroxyphenyl) fluorene and chloromethyl oxirane; in the compound of general formula (1), X is fluorene-9, 9-diyl, R ₁ to R ₄ are hydrogen compounds) AA: Acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Bromine Tetraethylammonium PGMEA: Propylene Glycol Monomethyl Ether Acetate

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

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

(Alkali-soluble resin containing unsaturated group) (A): The unsaturated group-containing alkali-soluble resin solution obtained in the above synthesis example (solid content concentration: 56.0% by mass)

(photopolymerizable monomer) (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Corporation, "Aronix" is a registered trademark of Toagosei Corporation)

(photopolymerization initiator) (C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime ) (Irgacure OXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of BASF Japan) (C)-2: Adeka arkls NCI-831, manufactured by Adeka Corporation, "Adeka arkls" is a registered trademark of Adeka Corporation)

(carbon black dispersion) (D): Carbon black concentration of 25.0 mass %, polymer dispersant concentration of 2.0 mass %, PGMEA dispersion liquid (solid content) of dispersing resin (alkali-soluble resin (A) of synthesis example (solid content: 8.0 mass %)) 35.0 mass %)

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

(Dispersant) (F)-1: DISPERBYK-140 (solid content concentration: 52 mass %) (F)-2: DISPERBYK-142 (solid content concentration: 60 mass %) (F)-3: DISPERBYK-9076 (solid content concentration: 100 mass %) (F)-4: DISPERBYK-167 (solid content concentration: 52 mass %) (F)-5: DISPERBYK-170 (solid content concentration: 30 mass %) (F)-6: DISPERBYK-180 (solid content concentration: 100 mass %) (F)-7: DISPERBYK-9077 (solid content concentration: 100% by mass) Furthermore, (F)-1 to (F)-7 are all manufactured by BYK-Chemie Japan, and "DISPERBYK" is a registered trademark of BYK-Chemie Japan.

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

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

[Table 1] Ingredients Example Example Example Example Example Example Example Example Example Example 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 value of F component 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

[evaluate] The light-shielding film which hardened the photosensitive resin composition for black resists for evaluation was produced as follows.

(Preparation of light-shielding film for evaluation) Using a spin coater, the photosensitive resin composition shown in Table 1 was applied on a pre-irradiated wavelength of 254 μm with a low-pressure mercury lamp so that the film thickness after heat curing treatment was 1.2 μm. On the glass substrate "#1737" (manufactured by Corning) (hereinafter, referred to as "glass substrate") of 125 mm x 125 mm, the surface of which was cleaned with ultraviolet rays with an illuminance of 1000 mJ/cm ² , using a heating The plate was pre-baked at 90° C. for 1 minute to produce a light-shielding film. Then, the exposure gap was adjusted to 100 μm, and a negative mask with line/space=10 μm/50 μm was covered on the dry light-shielding film, and 50 ^mJ / cm ² of ultraviolet light, the photosensitive part of the photohardening reaction.

Next, the light-shielding film after exposure was subjected to a development time (break time=BT) at 25° C. with a spray pressure of 1 kgf/cm ² with a 0.04% potassium hydroxide solution from the start of pattern development. After developing treatment for +10 seconds and +20 seconds, spray washing at 5 kgf/cm ² was performed to remove the unexposed portion of the light-shielding film to form a light-shielding film pattern on the glass substrate, using a hot air dryer at 230 ° C. The main hardening (post-baking) was performed for 30 minutes, and the light-shielding films for evaluation of Examples 1-10 and Comparative Examples 1-7 were obtained.

About the produced light-shielding film for evaluation, the following items were evaluated.

[Pattern linearity evaluation] (Evaluation method) For the 10 μm mask pattern after main hardening (post-baking), use an optical microscope and a scanning electron microscope (SEM) to observe the serration at the edge of the pattern. In addition, the evaluation of the pattern linearity was performed in the case of BT+10 second and the case of BT+20 second. In addition, ○ or more was set as a pass.

(Evaluation Criteria) ○: No zigzag pattern was observed at the edge of the pattern △: The edge of the pattern is partially serrated ×: It is confirmed that the pattern edge portion is zigzag throughout the whole

[Optical Density Evaluation] (Evaluation method) The optical density (optical density, OD) of the produced light-shielding film for evaluation was calculated|required using a Macbeth transmission densitometer. In addition, the film thickness of the light-shielding film formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was set to OD/μm.

The optical density (OD) was calculated by the following formula (1). Optical Density (OD)=-log ₁₀ T (1) (T represents transmittance)

[Reflectivity evaluation] (Evaluation method) About the board|substrate with a light-shielding film produced similarly to the light-shielding film for the said evaluation, the incident angle was measured using the ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.). 2° The reflectance on the substrate (glass substrate) side was measured. In addition, △ or more was set as a pass. (Evaluation Criteria) ○: The reflectance on the substrate side of the substrate with the light-shielding film is 5% or less △: The reflectance on the substrate side of the substrate with the light-shielding film is more than 5% and less than 6% ×: The reflectance on the substrate side of the substrate with the light-shielding film is 6% or more

[Assessment of Agglomerated Foreign Matter] (Evaluation method) The light-shielding film for evaluation after main curing (post-baking) was observed with an optical microscope, and the presence or absence of aggregated foreign matter was confirmed. In addition, △ or more was set as a pass.

(Evaluation Criteria) ○: Aggregated foreign matter was not observed in the light-shielding film △: Aggregated foreign matter was observed in a part of the light-shielding film ×: Aggregated foreign matter was observed on the entire surface of the light-shielding film

The evaluation results are shown in Table 2.

[Table 2] Ingredients Example Example Example Example Example Example Example Example Example Example 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 Reflectance / Substrate side (%) 4.8 (〇) 4.8 (〇) 4.9 (〇) 4.9 (〇) 4.8 (〇) 4.9 (〇) 5.5 (△) 4.8 (〇) 5.0 (〇) 5.6 (△) 4.8 (〇) 4.8 (〇) 4.8 (〇) 4.8 (〇) 4.8 (〇) 4.8 (〇) 4.9 (〇) Pattern linearity BT+10 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 △ △ 〇 〇 BT+20 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 × 〇 × × 〇 〇 Agglomerated foreign matter evaluation 〇 △ 〇 〇 〇 〇 〇 〇 〇 〇 × △ × 〇 〇 × ×

As shown in Examples 1 to 10, it was found that a high-definition pattern can be formed by using a dispersant having both an acid value and an amine value of 10 mgKOH/g or more and 80 mgKOH/g or less. On the other hand, when both the acid value and the amine value are more than 80 mgKOH/g, the solubility in the developing solution becomes too high, and the linearity of the pattern is thus degraded.

Moreover, as shown in Example 1 - Example 10, compared with the comparative example 2 and the comparative example 5 which applied only the dispersing agent which has an amine value, it turns out that the zigzag shape of a pattern edge part is eliminated. The reason for this is considered to be that the solubility in the developer tends to decrease by adsorbing the dispersant to the silica particles, but the application of a dispersant having an acid value and an amine value ensures that the silica particles are soluble in the developer. solubility in .

In addition, as shown in Examples 1 to 10, it was found that the dispersion stability of silica particles can be improved by using a dispersant having an acid value and an amine value of 10 mgKOH/g or more and 80 mgKOH/g or less. Suppresses the generation of agglomerated foreign matter. In particular, in Example 1 and Example 3 to Example 10 using a polymer dispersant having an alkylammonium salt structure, it was found that aggregation of foreign substances derived from silica particles can be significantly suppressed. The reason for this is considered to be that the silanol groups present on the surfaces of the silica particles are effectively protected by the dispersant, and the dispersion stability in the photosensitive composition for black resists is improved.

As shown in Examples 1 to 10, the ratio (m _F /m) of the total mass (m _F ) of the (F) dispersant to the total mass (m _E ) of the (E) silica particles was found _E ) When it is set to 0.02 to 0.6, the reflectance on the glass substrate side can be suppressed to 5% or less, and the aggregated foreign matter derived from the silica particles can be suppressed. If _mF / _mE is less than the above-mentioned range, the dispersion stability of the silica particles is insufficient, and aggregated foreign matter may be generated. On the other hand, when _mF / _mE is larger than the above-mentioned range, the compatibility of the silica particles becomes too high, so that it is not concentrated in the vicinity of the glass substrate, and the reflectance on the glass substrate side is more than 5%. [Industrial Availability]

According to the photosensitive resin composition of this invention, the photosensitive resin composition for black matrices which have both high light-shielding property and low reflectance, and the light-shielding film using the same, a color filter, and a touch panel can be provided. Moreover, according to the said color filter and a touch panel, various display apparatuses excellent in visibility can be provided.

without

Claims (10)

A photosensitive resin composition for a black resist, comprising: (A) a photosensitive resin containing an unsaturated group; (B) a photopolymerizable monomer having at least two or more unsaturated bonds; (C) photopolymerization an initiator; (D) at least one light-shielding component selected from the group consisting of black pigments, color mixing pigments, and light-shielding materials; (E) silica particles; and (F) a dispersant, the (F) dispersing agent The agent has an acid value and an amine value, the acid value and the amine value are both 10 mgKOH/g or more and 80 mgKOH/g or less, and the total mass (m _F ) of the (F) dispersant is relative to the ( E) The ratio (m _F /m _E ) of the total mass (m _E ) of the silica particles is 0.02 to 0.60. The photosensitive resin composition for black resists according to claim 1, wherein the (A) unsaturated group-containing photosensitive resin is a bisphenol-derived resin represented by the following general formula (1). An unsaturated group-containing photosensitive resin obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups with (meth)acrylic acid, and further reacting with a polyvalent carboxylic acid or its anhydride,

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9 represented by the general formula (2), 9-diradical or single bond, l is an integer from 0 to 10);

. The photosensitive resin composition for a black resist according to claim 1 or claim 2, wherein the (F) dispersant is a polymer compound having an alkylammonium salt structure. The photosensitive resin composition for a black resist according to claim 1 or claim 2, wherein the (E) silica particles have an average particle diameter of 1 nm to 100 nm. The photosensitive resin composition for a black resist according to claim 1 or claim 2, wherein the total mass (m _E ) of the (E) silica particles is relative to the total mass of the (D) light-shielding component. The ratio (m _E /m _D ) of the mass (m _D ) is 0.01 to 0.20. A method for producing a photosensitive resin composition for a black resist, comprising (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer, and (C) a photopolymerizable A starting agent, (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 are mixed, said (E) The silica particle dispersion contains (F) a dispersant, and the (F) dispersant has an acid value and an amine value, and the acid value and the amine value are both 10 mgKOH/g or more and 80 mgKOH/g or less, 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. A light-shielding film obtained by curing the photosensitive resin composition for a black resist according to any one of Claims 1 to 5. A color filter having the light-shielding film as claimed in 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.