KR20200115218A - Photosensitive resin composition for black resist, light-shielding layer cured thereof, and color filter with them - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a black resist having light shielding properties and low reflectance and a light shielding film and a color filter formed by hardening the same. The photosensitive resin composition for a black resist of the present invention comprises (A) a photosensitive resin containing an unsaturated group, (B) a photo-polymerizable monomer having at least two ethylenic unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from a black pigment, a color-mixed pigment and a light-shielding material and (E) silica particles. A silica particle for the component (E) is a hollow particle.

Description

A photosensitive resin composition for black resist, and a light-shielding film and color filter formed by curing the same TECHNICAL FIELD TECHNICAL FIELD [PHOTOSCENSITIVE RESIN COMPOSITION FOR BLACK RESIST, LIGHT-SHIELDING LAYER CURED THEREOF, AND COLOR FILTER WITH THEM}

The present invention relates to a photosensitive resin composition for a black resist, and a light shielding film and a color filter formed by curing the same.

In recent years, with the development of mobile terminals, display devices such as touch panels and liquid crystal panels used outdoors or on vehicles are increasing. In the display device, a light-shielding film is formed on an outline of the touch panel to block light leakage from a peripheral portion of the liquid crystal panel on the rear surface, and the liquid crystal panel has a color adjacent to each other to prevent light leakage from the screen during black display. A black matrix is formed in order to suppress the mixing of the resists.

In a display device, etc., in order to suppress light leakage and the like to improve the visibility of the screen of the display device, etc., the concentration of the black pigment in the light-shielding film is increased to increase the light-shielding property of the light-shielding film (lowering the light transmittance of the light-shielding film) in some cases . Since the refractive index of the black pigment is high compared to the refractive index of the transparent substrate or the curable resin, when the concentration of the black pigment in the light-shielding film is increased, the reflectance when viewed from the side opposite to the surface on which the light-shielding film of the transparent substrate is formed will increase. Therefore, reflection at the interface between the light shielding film formed on the transparent substrate and the transparent substrate increases, and a defect in which the black matrix boundary is prominent due to the difference in reflectance between the glare on the light shielding film and the color filter colored portion occurs.

For this reason, a photosensitive resin composition for black resists having both high light-shielding property and low reflectance, and a light-shielding film and color filter formed by curing the same are desired.

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

Japanese Patent Publication No. 2015-161815

However, when the present inventors studied, in the black photosensitive resin composition described in Patent Document 1, a light-shielding film having both high light-shielding property and low reflectance could not be obtained. In addition, in various display devices and light-shielding films for sensors such as solid-state imaging devices, depending on the design of the device configuration, not only the case where it is necessary to lower the reflectance of the light-shielding film applied to a transparent substrate such as glass on the transparent substrate side, but also a transparent substrate In some cases, it is required to reduce the reflectivity of the surface in contact with the surface opposite to the surface (hereinafter referred to as "coating surface").

The present invention has been made in view of these points, and an object of the present invention is to provide a photosensitive resin composition for black resists having high light-shielding properties and low reflectivity, and a light-shielding film and a color filter formed by curing the same.

The photosensitive resin composition for a black resist according to the present invention comprises (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a black pigment. , A photosensitive resin composition for black resists comprising at least one light-shielding component selected from a mixed color pigment and a light-shielding material, and (E) silica particles, wherein the silica particles as the component (E) are hollow particles.

The light shielding film according to the present invention is composed of the photosensitive resin composition for black resist.

The color filter according to the present invention has the light shielding film as a black matrix.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for black resist which has high light-shielding property and low reflectance, and a light-shielding film and a color filter using the same can be provided. Further, when the light-shielding film of the present invention is formed on a transparent substrate, it can contribute not only to low reflection on the transparent substrate side, but also to realize low reflection on the coated surface side of the light shielding film.

Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resists of the present invention (hereinafter, abbreviated as photosensitive resin composition) contains components (A) to (E). Hereinafter, (A)-(E) components are demonstrated.

((A) component)

(A) It is preferable that the unsaturated group-containing photosensitive resin as a component has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. If it is the said resin, it does not specifically limit and can be used widely.

Examples of the unsaturated group-containing photosensitive resin include an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter referred to as ``bisphenol type epoxy compound represented by general formula (1)''), (meth)acrylic acid. There is an epoxy (meth) acrylate acid adduct obtained by reacting a polybasic carboxylic acid or an anhydride thereof with a compound having a hydroxy group obtained by reacting. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin, or an equivalent thereof. In addition, "(meth)acrylic acid" is a generic term of acrylic acid and methacrylic acid, and it means one or both of these.

(A) It is preferable that the unsaturated group-containing photosensitive resin which is a component is a bisphenol type epoxy compound represented by General formula (1).

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

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. Since this reaction generally involves oligomerization of a diglycidyl ether compound, an epoxy compound containing two or more bisphenol skeletons is contained.

Examples of bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, and 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-hydroxyl) Phenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyl) Hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, Bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2, 2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3 -Methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9, 9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3- Fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9, 9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. are included. Among these, bisphenols having a fluorene-9,9-diyl group are preferable.

In addition, examples of the acid monoanhydride of (a) dicarboxylic acid or tricarboxylic acid in which a hydroxy group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid is reacted include chain hydrocarbon dicarboxylic acid. Acid monohydrides of acids or tricarboxylic acids, acid monohydrides of alicyclic dicarboxylic acids or tricarboxylic acids, acid monohydrides of aromatic dicarboxylic acids or tricarboxylic acids, and the like. Here, examples of the acid anhydride of a chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, Acid monohydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid are included. Further, an acid monohydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent group has been introduced is included. In addition, examples of the acid anhydride of alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, etc. Contains acid 1 anhydride of. Further, an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent group has been introduced is also included. Further, examples of the acid monohydride of an aromatic dicarboxylic acid or tricarboxylic acid include acid monohydrides such as phthalic acid, isophthalic acid, and trimellitic acid. Further, an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced is included.

In addition, examples of the acid anhydride of (a) dicarboxylic acid or tricarboxylic acid reacting with a hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include chain hydrocarbon dicarboxylic acid Acid monohydrides of acids or tricarboxylic acids, acid monohydrides of alicyclic dicarboxylic acids or tricarboxylic acids, acid monohydrides of aromatic dicarboxylic acids or tricarboxylic acids, and the like. Here, examples of the acid anhydride of a chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, Acid monohydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid are included. Further, an acid monohydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent group has been introduced is included. In addition, examples of the acid anhydride of alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, etc. Contains acid 1 anhydride of. Further, an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent group has been introduced is also included. Further, examples of the acid monohydride of an aromatic dicarboxylic acid or tricarboxylic acid include acid monohydrides such as phthalic acid, isophthalic acid, and trimellitic acid. Further, an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced is included.

The molar ratio of (a) dicarboxylic acid or tricarboxylic acid anhydride and (b) tetracarboxylic acid dianhydride reacted with epoxy (meth)acrylate (a)/(b) is 0.01 to 10.0. It is preferable, and it is more preferable that it is 0.02 or more and less than 3.0. If the molar ratio (a)/(b) is out of the above range, it is not preferable because the optimum molecular weight for obtaining a photosensitive resin composition having good light patterning property cannot be obtained. Further, the smaller the molar ratio (a)/(b) is, the higher the molecular weight and the alkali solubility tends to decrease.

In addition, the reaction of the epoxy compound and (meth)acrylic acid, and the reaction of the epoxy (meth)acrylate obtained in this reaction with the polybasic acid or its acid anhydride is not particularly limited, and a known method can be employed. In addition, the unsaturated group-containing photosensitive resin synthesized in the above reaction preferably has a weight average molecular weight (Mw) of 2000 to 10000, and an acid value of 30 to 200 mg/KOH.

Other examples of resins preferred as the unsaturated group-containing photosensitive resin as the component (A) include resins having a (meth)acryloyl group and a carboxyl group as a copolymer such as (meth)acrylic acid and (meth)acrylic acid ester. Examples of the resin include reacting (meth)acrylic acid to a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, and finally dicarboxylic acid or tricarboxylic acid An alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting an anhydride of The copolymer is 20 to 90 mol% of repeating units derived from diester glycerol esterified with (meth)acrylic acid, as shown in Japanese Patent Laid-Open No. 2014-111722, and one or more polymerizations copolymerizable therewith. A copolymer composed of 10 to 80 mol% of repeating units derived from a sexually unsaturated compound and having a number average molecular weight (Mn) of 2000 to 20,000 or an acid value of 35 to 120 mgKOH/g, and Japanese Patent Laid-Open No. 2018-141968 A weight average molecular weight (Mw) of 3000 to 500,000, an acid value of 30 to 200 mg, including a unit derived from the represented (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di or tricarboxylic acid residue An alkali-soluble resin containing a polymerizable unsaturated group, which is a /KOH polymer, can be referred to.

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

((B) component)

Examples of the photopolymerizable monomer having at least two ethylenically unsaturated bonds in the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , Tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, penta Erythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate Rate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, caprolactone modified dipentaerythritol (Meth)acrylic acid esters such as hexa(meth)acrylate, and resinous polymers having a (meth)acrylic group as a compound having an ethylenic double bond are included. Only one type of these monomers may be used alone, or two or more types may be used in combination. In addition, the photopolymerizable monomer having at least two ethylenically unsaturated bonds can serve to crosslink the molecules of the alkali-soluble resin containing, and in order to exhibit this function, it is recommended to use a photopolymerizable monomer having 3 or more photopolymerizable groups desirable. In addition, the acrylic 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 more preferably 80 to 200. In addition, (B) component does not have a free carboxyl group.

Examples of the resinous polymer having a (meth)acryloyl group as a compound having an ethylenic double bond that can be included in the composition as a component (B) include carbon-carbon in the (meth)acryloyl group of a polyfunctional (meth)acrylate. A dendritic polymer obtained by adding a polyvalent mercapto compound to a part of a double bond can be illustrated. Specifically, a resinous polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the general formula (3) with a polyvalent mercapto compound represented by the general formula (4), etc. are included.

(In formula (3), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the remainder of the n hydroxy groups in the k hydroxy groups of R ₇ (OH) _k donated to the ester bond in the formula. Preferred R ₇ ( OH)k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyhydric alcohol ether formed by linking a plurality of molecules of the polyhydric alcohol through an ether bond by dehydration and condensation of the alcohol. , Or an ester of a polyhydric alcohol or a polyhydric alcohol ether thereof and a hydroxy acid, k and n independently represent an integer of 2 to 20, but k≥n.)

(Formula (4) of, R ₈ represents a single bond or a hydrocarbon group of 2 to 6-valent C1~C6, m is 2 when R ₈ is unity sum, R ₈ is 2 to 6 valent when date integer from 2 to 6 to be)

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

Examples of the polyhydric mercapto compound represented by the general formula (4) include trimethylolpropane tri (mercaptoacetate), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercaptoacetate), pentaerythritol tri ( Mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.

The blending ratio of the component (A) and the component (B) is a weight ratio (A)/(B), preferably 30/70 to 90/10, and more preferably 60/40 to 80/20. If the blending ratio of the component (A) is 30/70 or more, the cured product after photocuring is difficult to soften, and the acid value of the coating film is less likely to be lowered in the unexposed portion, so that a decrease in solubility in an alkali developer can be suppressed. Therefore, it is difficult to produce a defect that the pattern edge becomes rough or does not become sharp. In addition, if the blending ratio of the component (A) is 90/10 or less, the ratio of the photoreactive functional group to the resin is sufficient, so that a desired crosslinked structure can be formed. In addition, since the acid value in the resin component is not too high, the solubility in the alkali developer in the exposed portion is difficult to increase, so that the formed pattern becomes thinner than the target line width or lack of the pattern can be suppressed.

((C) ingredient)

(C) Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. Benzophenones such as acetophenones, benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluoro Biimidazoles such as phenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole Compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloro Halomethylthiazole compounds such as romethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl-1,3,5-triazine, 2- (4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 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-tri Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1, Halomethyl-S-triazine compounds such as 3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-( 4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyl O-acyloxime compounds such as oxime; benzyl dimethyl ketal, thioxanthone, 2-chloro thioxanthone, 2,4-diethyl thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone Sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; anthraquinones such as azobisisobutylonitrile, benzoyl peroxide, and Organic peroxides such as menperoxide; Thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, and 2-mercaptobenzothiazole, tertiary amines such as triethanolamine and triethylamine, etc. These photopolymerization initiators may be used alone or in combination of two or more.

In particular, in the case of a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxime compounds (including ketooxime). Examples of the group of compounds that can be preferably used include O-acyloxime photopolymerization initiators represented by the general formulas (5) and (6). Also in these compound groups, when using a coloring agent at a high concentration of a colorant and when forming a light shielding film pattern, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient of 10000 or more at 365 nm. In addition, the "photoinitiator" as used in the present invention is used in the sense including a sensitizer.

(In formula (5), R ₉ and R ₁₀ each independently represent a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group or a C4 to C12 heterocyclic group, and R ₁₁ is C1 to Represents a C15 alkyl group, a C6 to C18 aryl group, and a C7 to C20 arylalkyl group, wherein the alkyl group and aryl group are C1 to C10 alkyl groups, C1 to C10 alkoxy groups, C1 to C10 alkanoyl groups, and halogens. It may be substituted, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and the alkyl group may be a linear, branched, or cyclic alkyl group.)

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

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

((D) component)

The light-shielding components such as black pigment, mixed color organic pigment, and light-shielding material of the component (D) that can be used in the present invention have an average particle diameter of 1 to 1000 nm (a laser diffraction/scattering method particle size distribution meter or a dynamic light scattering method particle size distribution meter). Average particle diameter), a known light-shielding component can be used without particular limitation.

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

Examples of the mixed color organic pigment of the component (D) include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, sren pigments, perylenes Pigments in which at least two colors are mixed selected from organic pigments such as pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are included.

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

In addition, in the case of using a mixed color organic pigment as the (D) component, examples of the organic pigments usable include those of the following numbers as a color index name, but are not limited thereto.

Pigment red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.

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

Pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.

Pigment green 7, 36, 58, etc.

Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

Pigment violet 19, 23, 37, etc.

The blending ratio of the light-shielding component of the component (D) can be arbitrarily determined by the desired light-shielding degree, but it is preferably 20 to 80 mass%, more preferably 40 to 70 mass%, based on the solid component in the photosensitive resin composition. Do. As the light-shielding component of the component (D), when an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black is used, it is 40 to 60% by mass relative to the solid component in the photosensitive resin composition. It is particularly preferred. When the light-shielding component is 20 mass% or more with respect to the solid component in the photosensitive resin composition, sufficient light-shielding property can be obtained. When the light-shielding component is 80% by mass or less with respect to the solid component in the photosensitive resin composition, since the content of the photosensitive resin serving as the original binder does not decrease, desired developing characteristics and film-forming ability can be obtained.

The component (D) is a light-shielding component dispersion dispersed in a solvent, and is usually mixed with other compounding components, and a dispersant can be added in that case. As the dispersant, a known compound (a compound commercially available under the name of a dispersant, a dispersion wetting agent, a dispersion accelerator, etc.) used for dispersing a pigment (light-shielding component) can be used without particular limitation.

Examples of the dispersant include a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative type dispersant (dispersing aid). In particular, the dispersant has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point on the colorant, and the amine value is 1 to 100 mgKOH/g, It is preferable that the average molecular weight (Mn) is a cationic polymer-based dispersant in the range of 1000 to 100000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the light-shielding component. In addition, high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but those that do not have dispersion promoting ability are not treated as dispersants. However, it does not limit its use for the purpose of stabilizing dispersion.

((E) component)

(E) The silica particle which is a component is a manufacturing method which made gas-phase reaction or liquid-phase reaction, and shape (spherical shape, non-spherical shape) in particular is not limited.

It is preferable that the silica particle which is the (E) component used in this invention is a hollow silica particle. In addition, "hollow silica particle" is a silica particle which has a cavity inside a particle.

Like the silica particles described above, since the silica particles containing gas in the particles have high dispersibility, the pattern linearity of the cured film (light shielding film) obtained by curing the photosensitive resin composition of the present invention is improved. In addition, by using silica particles containing a gas in the 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 40 to 100 nm, more preferably 50 to 80 nm. When the average particle diameter is within the above range, the mechanical strength of the silica particles themselves is high, so that even if the particles are hollow, it is difficult to break. In addition, compared with the case of a small particle diameter of several nm, it is considered that aggregation of silica particles is difficult to occur in a size within the above range. Accordingly, in the range of the particle diameter, the silica particles are excellent in dispersion stability, and thus may be uniformly present in the light shielding film. Therefore, it is difficult to cause variation in reflectance on the light-shielding film.

In addition, when it is in the above range, the ratio of the voids inside the silica particles (hereinafter referred to as porosity) can also be adjusted. Since the silica particles have a different refractive index depending on the size of the particle diameter, it is easy to adjust the refractive index of the light shielding film regardless of the material of the transparent substrate. In addition, the "porosity" is the ratio of the cavity part in the particle|grains occupied by a particle.

The average particle diameter of the silica particles can be obtained by selecting 100 particles at random, measuring the major axis length and the minor axis length of the particles, and using the above averages. In addition, the average particle diameter of the silica particles can be measured by the Cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) of the dynamic light scattering method. .

Further, the refractive index of the silica particles is preferably 1.10 to 1.41, more preferably 1.10 to 1.35. By using the silica particles having a refractive index lower than that of the general silica particles (1.45 to 1.47), the refractive index of the light shielding film can be lower than that of the light shielding film including only general silica particles.

Further, the refractive index of the silica particles can be obtained from a transparent mixture obtained by treating the silica particles in a powder form and mixing a standard refractive solution having a known refractive index. In this case, the refractive index of the standard refractive solution of the mixed solution is referred to as the refractive index of the silica particles. In addition, the refractive index of the silica particles can be measured using an Abbe refractometer.

Since the silica particles have a higher porosity, the lower the refractive index, so the porosity of the silica particles is preferably 20% by volume or more, preferably 20 to 95% by volume, and more preferably 25 to 90% by volume. It is more preferable that it is 30 to 90 volume%, and it is especially preferable that it is 35 to 90 volume%. When the porosity is within the above range, a light shielding film having a desired refractive index can be easily obtained. Further, since reflection caused by a difference in refractive index of the light-shielding film formed of a transparent substrate can be suppressed, reflection can be suppressed even if an antireflection film or the like is not separately provided on the substrate.

In addition, by making the porosity of the silica particles within the above range, the weight of the silica particles can be made lighter than that of ordinary silica particles. From this, it is considered that the silica particles, unlike ordinary silica particles, become difficult to settle toward the transparent substrate side even in a state applied in the photosensitive resin composition and on the transparent substrate. Accordingly, since the silica particles are uniformly dispersed in the light shielding film, not only the reflectance when viewed from the transparent substrate side, but also the reflectance when viewed from the cured film side (the light shielding film surface side) can be lowered.

The porosity of the silica particles can be determined by using a transmission electron microscope. Since the cavity portion of the silica particles has a low density and the contrast of the cavity portion is lowered in a transmission electron microscope photograph, the outer portion and the cavity portion of the silica particles can be confirmed. From the above micrograph, the longest and shortest diameters of the silica particles are first measured, and the average value is the particle diameter of the particles, and the volume V ₁ assuming that the particle shape is a spherical shape is obtained. Subsequently, the longest and shortest diameters of the cavity portion of the particle are measured, and the average value is used as the diameter of the cavity, and the volume V ₂ assuming that the shape of the cavity is a spherical shape is obtained. The porosity can be expressed as the ratio of the volume V ₂ to the volume V ₁ .

As described above, the shape of the silica particles is not particularly limited as long as it has a desired porosity. It may be a spherical shape or an elliptical shape. It is preferable that the shape of the silica particles used in the present invention is a spherical shape.

It is preferable that the silica particles have a sphericity of 1.05 to 1.5. When the sphericity of the silica particles is within this range, the particle shape becomes close to the sphericity. For this reason, it is possible to uniformly fill the light-shielding film with a thin film thickness, and a light-shielding film in which the silica particles are not exposed to the outside from the film surface can be formed while maintaining the film surface smoothness. 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 and the shortest diameter of the particles (an average value of 100 arbitrary silica particles). Here, the longest diameter and shortest diameter of the silica particles are values 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 micrograph.

By mixing and dispersing the components (A) to (E) by an appropriate method, a dispersion liquid for use in the photosensitive resin composition of the present invention can be prepared.

(solvent)

In the photosensitive resin composition of the present invention, it is preferable to use a solvent which is a component (F) other than the components (A) to (E). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Glycol ethers such as monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Acetic acid esters of are included. By dissolving and mixing these alone or in combination of two or more, a uniform solution-form composition can be obtained.

In addition, the photosensitive resin composition of the present invention includes resins other than the component (A) such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than hollow silica, leveling agents, defoaming agents, and interfacial agents, if necessary. Additives, such as an activator and a coupling agent, can be blended.

Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, and the like. Examples of plasticizers include dibutylphthalate, dioctylphthalate, tricresyl phosphate, and the like. Examples of fillers include glass fibers, silica, mica, alumina, and the like. Examples of the antifoaming agent and the leveling agent include silicone, fluorine, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the coupling agent include 3-(glycidyloxy)propyl trimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane. This includes.

The photosensitive resin composition of the present invention contains at least two of the unsaturated group-containing photosensitive resin as the component (A) and the component (B) in the solid content excluding the solvent as the component (F) (the solid content includes a monomer that becomes a solid content after curing). It is preferable that the photopolymerizable monomer having two ethylenically unsaturated bonds, (C) a photopolymerization initiator as a component, a light-shielding component as a (D) component, and (E) hollow silica particles are contained in a total of 80% by mass or more, It is more preferable to contain 90 mass% or more. The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass based on the total amount.

In addition, the light-shielding film formed by curing the photosensitive resin composition of the present invention is obtained by, for example, applying a solution of the photosensitive resin composition to a substrate, drying the solvent, and curing by irradiating light (including ultraviolet rays, radiation, etc.) Lose. Using a photomask or the like, a desired pattern is obtained by forming a light-touched portion and a non-contacting portion, curing only the light-touched portion and dissolving the other portion with an alkaline solution.

In addition, in the color filter having the light-shielding film of the present invention as a black matrix, for example, a light-shielding film having a thickness of 1.0 to 2.0 μm is formed on a transparent substrate, and red, blue, and green pixels are formed by photolithography after forming the light-shielding film. It is produced by forming, and also by inserting red, blue, and green inks into the light-shielding film by an ink jet process.

Further, the light shielding film formed by curing the photosensitive resin composition of the present invention can also be used as a black column spacer of a liquid crystal display device. For example, a single black resist may be used to fabricate a plurality of portions having different film thicknesses, one may function as a spacer, and the other may function as a black matrix.

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

As a method of applying the photosensitive resin composition to the substrate, any method such as a known solution immersion method, a spray method, a roller coater, a land coater, a slit coater or a spinner may be employed. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking is performed by heating with an oven, a hot plate, or the like, vacuum drying, or a combination thereof. The heating temperature and heating time in prebaking can be appropriately selected depending on the solvent to be used, but, for example, it is preferably performed at 80 to 120°C for 1 to 10 minutes.

As the radiation used for exposure, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, and the like can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. As a developer suitable for this alkaline development, for example, an aqueous solution such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide can be used. These developing solutions can be appropriately selected in accordance with the properties of the resin layer, but it is also effective to add a surfactant if necessary. The developing temperature is preferably 20 to 35°C, and a fine image can be precisely formed by using a commercially available developer or ultrasonic cleaner. In addition, after alkali development, it is usually washed with water. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid storage) developing method, or the like can be applied.

In this way, after developing, heat treatment (post-baking) is performed at 180 to 250°C for 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film (light shielding film) and the substrate. Like prebaking, this is done by heating with an oven, a hot plate, or the like.

In this way, the patterned cured film (light-shielding film) of the present invention is formed through each process by photolithography, and polymerization or curing (sometimes called curing by combining both) is completed by heat, and a desired pattern It is possible to obtain a light shielding film having.

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

The photosensitive resin composition for black resists of the present invention can be suitably used as a coating material. In particular, the ink for a color filter used in a liquid crystal display device or an image pickup device, and a light shielding film formed therefrom are useful as a color filter, a black matrix for liquid crystal projection, and the like. In addition, in addition to the color filter ink of a color liquid crystal display, the photosensitive resin composition for a black resist of the present invention is used in various multicolor displays such as organic electroluminescent devices, color liquid crystal displays, color facsimiles, image sensors, etc. typified by organic EL elements. It can also be used as an ink material for color fractionation or light-shielding. 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 emission from the element when used in, for example, an organic EL element can be reduced. . That is, it is possible to improve the contrast of the spot by reducing reflection of external light, and 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 thereto.

First of all, explanation is given from the synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin as the component (A), but the evaluation of the resin in these synthesis examples was performed as follows, unless rejected.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and then heated at 160° C. for 2 hours [W ₂ (g)]. Saved from food.

Solid content concentration (% by 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.) to obtain.

[Molecular Weight]

Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSK gel Super H-2000 (2) + TSK gel Super H-3000 (1) + TSK gel Super H-4000 (1 piece) + TSK gel Super H-5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40°C, speed: 0.6 ml/min), measured with standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer) Kit) The weight average molecular weight (Mw) was calculated|required as a conversion value.

[Average particle diameter]

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

[Refractive index]

The refractive index of the silica particles was determined using an Abbe refractometer.

[Porosity]

In addition, the porosity of the silica particles was determined using a transmission electron microscope.

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

BPFE: Reaction of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In the compound represented by the general formula (1), X is fluorene-9,9-diyl, and R ₁ and R ₂ are hydrogen.

AA: acrylic acid

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

THPA: tetrahydro phthalic 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 added to a 500 ml four-necked flask equipped with a reflux condenser, followed by stirring at 100 to 105°C for 20 hours to react. Made it. Subsequently, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask, followed by stirring at 120 to 125°C for 6 hours to obtain an alkali-soluble resin (A) containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 56.1 mass%, the acid value (in terms of solid content) was 103 mgKOH/g, and Mw by GPC analysis was 3600.

The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared by the blending amount (numerical value by mass%) shown in Table 1. The compounding components used in the table are as follows.

(Alkaline-soluble resin containing polymerizable unsaturated groups)

(A): Alkali-soluble resin solution obtained in Synthesis Example (solid content concentration 56.1% by mass)

(Photopolymerizable monomer)

(B): Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (ARONIX M-405, manufactured by Toagosei Co., Ltd., "ARONIX" is a registered trademark of the company)

(Photopolymerization initiator)

(C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (Irgacure OXE-02, BASF Japan Ltd., "Irgacure" is a registered trademark of the company)

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

(Carbon Black Dispersion)

(D): PGMEA dispersion with a carbon black concentration of 25.0 mass% and a polymer dispersant concentration of 10.0 mass% (solid content 34.8 mass%)

(Silica dispersion)

(E)-1: Hollow silica isopropanol dispersion sol

(Manufactured by JGC Catalysts and Chemicals Ltd., solid content 20% by weight, average particle diameter about 50 nm, porosity 30% by volume, refractive index 1.30)

(E)-2: Hollow silica isopropanol dispersion sol

(Manufactured by JGC Catalysts and Chemicals Ltd., solid content 20% by weight, average particle diameter about 60 nm, porosity 37% by volume, refractive index 1.25)

(E)-3: Hollow silica isopropanol dispersion sol

(Manufactured by JGC Catalysts and Chemicals Ltd., solid content 20% by weight, average particle diameter about 75 nm, porosity 46% by volume, refractive index 1.21)

(E)-4: Hollow silica PGMEA dispersion sol

(JGC Catalysts and Chemicals Ltd. product, solid content 20% by weight, average particle diameter about 75 nm, porosity 46% by volume, refractive index 1.25)

(E)-5: solid silica isopropanol disperse sol

(Manufactured by Nissan Chemical Corporation, solid content 30% by weight, average particle diameter about 80 nm, porosity 0% by volume, refractive index 1.46)

(solvent)

(F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

(F)-2: Cyclohexanone (ANON)

[Example]

The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared in the blending amount (number of parts by mass) shown in Table 1. The compounding components used in the table are as follows. In addition, (F)-1 and (F)-2 are amounts which do not contain the solvent of (A) and (D)-4 and the solvent in (E).

[evaluation]

The following evaluation was performed using the photosensitive resin composition for black resists of Examples 1-5 and Comparative Examples 1 and 2.

(Preparation of a cured film (light shielding film) for evaluation of developing characteristics)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 with a low pressure mercury lamp to clean the surface of a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter, (Referred to as "glass substrate"), it was applied using a spin coater so that the film thickness after heat curing treatment became 1.2 µm, and prebaked at 90°C for 1 minute using a hot plate to prepare a hard film (light shielding film). . Subsequently, the exposure gap was adjusted to 100 μm, a negative photomask of line/space=10 μm/50 μm was placed on the dry light-shielding film, and UV rays of 50 mJ/cm 2 were irradiated with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm 2 Then, a photocuring reaction of the photosensitive portion was performed.

Subsequently, the exposed cured film (light-shielding film) was subjected to a shower pressure of 1 kgf/cm 2 at 25°C with a 0.04% potassium hydroxide solution, and +10 seconds and + from the development time (break time = BT) at which the pattern begins to appear. After performing the development treatment for 20 seconds, spray water washing of 5 kgf/cm 2 was performed, the unexposed portion of the cured film (light shielding film) was removed to form a cured film pattern on the glass substrate, and at 230°C using a hot air dryer. For 30 minutes, the cured film (light shielding film) according to Examples 1 to 5 and Comparative Examples 1 and 2 was obtained by main curing (post-baking).

About the cured film (light-shielding film) obtained by curing the photosensitive resin composition for black resists of Examples 1 to 5 and Comparative Examples 1 and 2 obtained above, the evaluation results of the following items are shown in Table 2.

[Development characteristics evaluation]

(Pattern line width)

(Assessment Methods)

The pattern line width after main curing (post-baking) was measured using a measuring microscope "XD-20" (manufactured by Nikon Corporation) to measure the pattern line width with a mask width of 10 µm. In addition, evaluation of the pattern line width was performed in the case of BT+10 second and the case of BT+20 second.

(Evaluation standard)

○: The pattern line width is within the range of 10±2 μm

×: The pattern line width is outside the range of 10±2 μm

(Pattern linearity)

(Assessment Methods)

A 10 µm mask pattern of main curing (post-baking) was observed using an optical microscope. In addition, evaluation of 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 the pass.

(Evaluation standard)

○: It is not confirmed that the pattern edge portion becomes rough

△: It is confirmed in part that the pattern edge part becomes rough

X: Roughness of the pattern edge portion is confirmed throughout

(Creation of a cured film (light shielding film) for optical density (OD) evaluation)

The photosensitive resin composition shown in Tables 1 and 2 was previously irradiated with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 with a low pressure mercury lamp to clean the surface of 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) ( Hereinafter, it is referred to as "glass substrate"), coated with a spin coater so that the film thickness after heat curing treatment becomes 1.1 μm, and prebaked at 90° C. for 1 minute using a hot plate to form a hard film (light shielding film). did. A photocuring reaction was carried out by irradiating ultraviolet rays of 50 mJ/cm 2 with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 without covering a negative photomask.

Subsequently, the exposed cured film (light-shielding film) was developed at 25°C with a 0.05% potassium hydroxide solution at a shower pressure of 1 kgf/cm 2, from the development time (break time = BT) to the beginning of the pattern appearing for 60 seconds. After performing 5 kgf/cm 2 spray water, removing the unexposed portion of the cured film (light shielding film) to form a cured film pattern on the glass substrate, and using a hot air dryer at 230°C for 30 minutes It cured (post-baked) to obtain a cured film (light shielding film) according to Examples 1 to 5 and Comparative Examples 1 and 2.

[Optical concentration evaluation]

(Assessment Methods)

The optical density (OD) of the produced cured film (light shielding film) was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the cured film (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 the transmittance)

[Reflectance evaluation]

(Assessment Methods)

With respect to the substrate with the cured film (light-shielding film) produced in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, using the ultraviolet visible infrared spectral intensity ``UH4150'' (manufactured by Hitachi High-Tech Corporation) at an incidence angle of 2°. Each reflectance of the cured film (light shielding film) side and the substrate (glass substrate) side was measured.

In the photosensitive resin compositions for black resists of Examples 1 to 5, it was confirmed that the reflectance can be reduced compared to a system in which silica does not exist (Comparative Example 1). Further, it was confirmed that low reflection could be achieved not only on the glass substrate side but also on the coating film (light-shielding film) side as compared with a system using silica that is not hollow (Comparative Example 2). In addition, since the cured films (light shielding films) formed by curing the photosensitive resin compositions for black resists of Examples 1 to 5 have good pattern linearity, the hollow silica is uniformly dispersed in the cured film compared to the system using solid silica. It was also suggested that it was done.

According to the photosensitive resin composition of the present invention, a photosensitive resin composition for black resists having high light-shielding properties and low reflectivity, and a light-shielding film and color filter using the same can be provided. In addition, when the light-shielding film of the present invention is formed on a transparent substrate, it can contribute to not only low reflection on the transparent substrate side, but also to realize low reflection on the applied surface side of the light shielding film. It is useful for light shielding films for sensors.

Claims (7)

(A) an unsaturated group-containing photosensitive resin, and
(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, and
(C) a photopolymerization initiator, and
(D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material, and
(E) As a photosensitive resin composition for black resists containing silica particles,
The silica particles as the component (E) are hollow particles, and the photosensitive resin composition for black resists. The method of claim 1,
In the (A) unsaturated group-containing photosensitive resin, a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the general formula (1) and (meth)acrylic acid is mixed with a polybasic carboxylic acid or an anhydride thereof. A photosensitive resin composition for black resists which is an unsaturated group-containing photosensitive resin obtained by further reacting.

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

The method according to claim 1 or 2,
The (E) silica particles have an average particle diameter of 40 to 100 nm, which is a photosensitive resin composition for black resists. The method according to any one of claims 1 to 3,
(E) The photosensitive resin composition for black resists having a porosity of 20% by volume or more of the silica particles. The method according to any one of claims 1 to 4,
The (E) silica particles have a refractive index of 1.10 to 1.41, which is a photosensitive resin composition for black resist. A light shielding film formed by curing the photosensitive resin composition for black resists according to any one of claims 1 to 5. A color filter comprising the light shielding film according to claim 6 as a black matrix.