KR20230047314A - Photosensitive resin composition, cured film thereof, and color filter, touch panel and display device with the same - Google Patents

Abstract

Provided is a photosensitive resin composition, which has both the desired light blocking properties and reflectance, and in forming a pattern, can obtain a cured film without jagged edges at the edge of the pattern. The photosensitive resin composition contains (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, mixed color pigments, and light-shielding materials, and (E) fine particles with a refractive index of 1.50 or more and 1.80 or less.

Description

Photosensitive resin composition, cured film, color filter, touch panel and display device

The present invention relates to a photosensitive resin composition, a cured film, a color filter, a touch panel, and a display device.

In recent years, with the development of mobile terminals, display devices such as touch panels and liquid crystal panels used outdoors or in vehicles are increasing. In the display device, a light blocking film is formed on the outer frame of the touch panel to block light leakage at the periphery of the liquid crystal panel on the rear side, and the liquid crystal panel is adjacent to each other to suppress light leakage from the screen during black display. In order to suppress color mixing between color resists to be performed, a black matrix, which is one type of light shielding film, is formed.

In a display device or the like, in order to improve the visibility of the screen of the display device or the like by suppressing light leakage or the like, there is a case in which the concentration of a black pigment in the light-shielding film is increased to increase the light-shielding property (lower the light transmittance of the light-shielding film). there is. Compared to the refractive index of the transparent substrate or the curable resin, the refractive index of the black pigment is high, so if 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 is formed of the transparent substrate increases. Therefore, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and the black matrix boundary is conspicuous due to projection onto the light-shielding film or difference in reflectance with the color filter colored portion. Problem occurs.

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

For example, Patent Document 1 discloses a black photosensitive resin composition characterized by containing hydrophobic silica fine particles and a specific dispersing agent (urethane-based dispersing agent). This is said to be able to form a black matrix that achieves both high light-shielding properties and low reflectance by using hydrophobic silica fine particles and a specific dispersing agent.

Japanese Unexamined Patent Publication No. 2015-161815

However, when the present inventors studied, the black photosensitive resin composition described in Patent Literature 1 has both desired light-shielding properties and reflectances, and in pattern formation, in pattern formation, when a light-shielding film cannot be obtained. there was

The present invention has been made in view of these points, and has a high light-shielding property and low reflectance, a photosensitive resin composition capable of forming a high-definition pattern, a cured film obtained by curing the same, a color filter and a touch panel having the cured film, and the color It is an object of the present invention to provide a display device having a filter and a touch panel.

That is, the gist of the present invention is as follows.

(1) (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound having at least two or more unsaturated bonds, (C) a photopolymerization initiator, and (D) a black pigment, a mixed color pigment, and a light-shielding material selected from The photosensitive resin composition containing at least 1 sort(s) of light-shielding component and (E) microparticles|fine-particles of refractive index 1.50-1.80.

(2) The photosensitive resin composition according to (1), wherein the fine particles (E) are aluminum oxide particles.

(3) The photosensitive resin composition according to (1) or (2), wherein the fine particles (E) have an average particle diameter of 10 to 300 nm.

(4) The photosensitive resin composition according to any one of (1) to (3), wherein the proportion of the fine particles (E) in the solid content is from 1 to 30% by mass.

(5) A cured film having a film thickness of 1 μm obtained by curing the photosensitive resin composition with light has a light-shielding degree OD [μm ^-1 ] of 2.6 or more, and a reflectance [%] of the cured film is 6.5 or less, and of the cured film The photosensitive resin composition according to any one of (1) to (4), wherein the value obtained by dividing the reflectance by the light-shielding degree OD is less than 1.65.

(6) A cured film formed by curing the photosensitive resin composition according to any one of (1) to (5).

(7) The color filter which has the cured film of (6) as a black matrix.

(8) The touch panel which has the cured film as described in (6) as a black matrix.

(9) A display device having the color filter according to (7) or the touch panel according to (8).

According to the present invention, a photosensitive resin composition capable of obtaining a cured film having high light-shielding properties and low reflectance, a cured film formed by curing the same, a color filter and touch panel having the cured film, and a display device having the color filter and touch panel can do.

Hereinafter, the present invention will be described in detail.

The photosensitive resin containing an unsaturated group as component (A) according to the present embodiment preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and contains both a polymerizable unsaturated group and a carboxyl group. it is more preferable It is not specifically limited as long as it is the said resin, It can use widely.

Examples of the unsaturated group-containing photosensitive resin include an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter, also referred to as "bisphenol-type epoxy compound represented by the general formula (1)"), (meth)acrylic acid There is an epoxy (meth)acrylate acid adduct obtained by reacting a polybasic carboxylic acid or its anhydride with a compound having a hydroxyl group. 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 general term for acrylic acid and methacrylic acid, and means one or both of these.

(A) It is preferable that the photosensitive resin containing an unsaturated group which is a component is a bisphenol-type epoxy compound represented by General formula (1). By employing the bisphenol-type epoxy compound represented by the general formula (1), good developing characteristics can be obtained.

[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-di represented by general formula (2) It is a diary or a single bond, and l is an integer of 0-10.

[Formula 2]

The bisphenol-type epoxy compound represented by General Formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. Since oligomerization of a diglycidyl ether compound is generally accompanied at the time of this reaction, the epoxy compound containing 2 or more bisphenol skeletons is included.

Examples of the bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl) )ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxy hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4- Hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane , bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2 ,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy- 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, Bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9 , 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3 -Fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9 , 9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol , 3,3'-biphenol, and the like. Among them, bisphenols having a fluorene-9,9-diyl group are preferred.

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

Further, as the acid dianhydride of (b) tetracarboxylic acid reacted with epoxy (meth)acrylate, acid dianhydride of chain hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, or aromatic tetracarboxylic acid dianhydride Acid dianhydrides of carboxylic acids are used. Here, examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Furthermore, the acid dianhydride of tetracarboxylic acid into which arbitrary substituents were introduce|transduced, etc. are contained. Moreover, examples of acid dianhydrides of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Acid dianhydrides such as Furthermore, the acid dianhydride of tetracarboxylic acid into which arbitrary substituents were introduce|transduced, etc. are contained. Moreover, acid dianhydrides, such as a pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid, are contained as an example of the acid dianhydride of aromatic tetracarboxylic acid. Furthermore, the acid dianhydride of tetracarboxylic acid into which arbitrary substituents were introduce|transduced, etc. are contained.

The molar ratio (a)/(b) of the acid monohydride of (a) dicarboxylic acid or tricarboxylic acid and the acid dianhydride of (b) tetracarboxylic acid reacted with epoxy (meth)acrylate is 0.01 or more and 10.0 It is preferable that it is below, and it is more preferable that it is 0.02 or more and less than 3.0. When the molar ratio (a)/(b) deviates from the above range, it is not preferable because the optimum molecular weight for forming a photosensitive resin composition having good light patterning properties cannot be obtained. Further, the smaller the molar ratio (a)/(b), the larger the molecular weight and the lower the alkali solubility.

In addition, the reaction between the epoxy compound and (meth)acrylic acid and the reaction between the epoxy (meth)acrylate obtained in this reaction and the polybasic carboxylic acid or its acid anhydride are not particularly limited, and a known method can be employed. . Moreover, as for the unsaturated group containing photosensitive resin synthesize|combined by the said reaction, as for the weight average molecular weight (Mw), 2000-10000 are preferable, and it is preferable that the acid value is 30-200 mg/KOH. In addition, the weight average molecular weight (Mw) can be measured using, for example, gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). In addition, the acid value can be titrated with a 1/10 N-KOH aqueous solution using, for example, a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Other examples of resins suitable as the unsaturated group-containing photosensitive resin as component (A) include copolymers of (meth)acrylic acid and (meth)acrylic acid ester, which have a (meth)acryloyl group and a carboxyl group. As an example of the resin, (meth)acrylic acid is reacted with a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, and finally dicarboxylic acid or tricarboxylic acid Alkali-soluble resins containing a polymerizable unsaturated group obtained by reacting an anhydride of a boxylic acid are included. The copolymer contains 20 to 90 mol% of repeating units derived from diesterglycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, as shown in Japanese Unexamined Patent Publication No. 2014-111722, and 1 copolymerizable with this A copolymer composed of 10 to 80 mol% of repeating units derived from a polymerizable unsaturated compound having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g, and Japanese Unexamined Patent Publication 2018- 141968, containing a unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di- or tricarboxylic acid residue, having a weight average molecular weight (Mw) of 3000 to 50000, an acid value Reference can be made to an alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer of 30 to 200 mg/KOH.

It is preferable that it is 10 mass % or more and 90 mass % or less with respect to the total mass of solid content, and, as for content of (A) component, it is more preferable that it is 20 mass % or more and 80 mass % or less. (A) When the said content of component is 10 mass % or more, it becomes possible to form a high-resolution pattern.

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

Examples of the photopolymerizable compound having at least two or more unsaturated bonds in the component (B) according to the present embodiment include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. (meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, tripropylene glycol diacrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Erythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa( (meth)acrylic acid esters such as meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth) ) Epoxy (meth)acrylates such as acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; Examples of the compound having an ethylenic double bond include a dendritic polymer having a (meth)acrylic group and the like. One type of these photopolymerizable compounds may be used alone, or two or more types may be used in combination. In addition, the photopolymerizable compound having at least two ethylenically unsaturated bonds can play a role of crosslinking the molecules of the polymerizable unsaturated group-containing alkali-soluble resin, and in order to exhibit this function, three unsaturated bonds It is preferable to use those having the above. Moreover, it is preferable that the acrylic equivalent obtained by dividing the molecular weight of the photopolymerizable compound by the number of (meth)acrylic groups in one molecule is 50 to 300, and the acrylic equivalent is more preferably 80 to 200. In addition, (B) component does not have a free carboxyl group.

The blending ratio of component (A) and component (B) is weight ratio (A)/(B), preferably 30/70 to 90/10, and more preferably 60/40 to 80/20. When 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 in the unexposed area is less likely to decrease, so the decrease in solubility in an alkaline developer can be suppressed. . Therefore, it is difficult to cause a problem that the pattern edge is jagged or does not become sharp. Moreover, since the ratio of the photoreactive functional group occupied in resin is sufficient as the compounding ratio of (A) component is 90/10 or less, a desired crosslinked structure can be formed. In addition, since the acidity of the resin component is not too high, the solubility in the alkaline developer in the exposed portion is difficult to increase, so that the formed pattern is thinner than the target line width and the pattern is missing. .

Examples of the photopolymerization initiator as component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- acetophenones such as butyl acetophenone, benzophenones such as 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-acyloxanthone compounds such as oximes: benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc. Anthraquinones: azobisisobutyronitrile, benzoyl peroxide, quinones Organic peroxides such as menperoxide include thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. These photoinitiators may be used alone or in combination of two or more.

Examples of the O-acyloxime-based compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by the general formulas (3) and (4). Also in these compound groups, when using a light-shielding component in high concentration, it is preferable to use the O-acyloxime system photoinitiator whose molar extinction coefficient in 365 nm is 10000 or more. In addition, "photoinitiator" as used in the present invention is used by the meaning containing a sensitizer.

[Formula 3]

In formula (3), R ₅ and R ₆ are each independently a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group, or a C4-C12 heterocyclic group, and R ₇ is C1 to C15 alkyl group, C6 to C18 aryl group, or C7 to C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkanoyl group, or a halogen, and the alkylene moiety is an unsaturated bond, an ether bond, a thioether bond, or an ester A bond may be included. Moreover, any linear, branched or cyclic alkyl group may be sufficient as an alkyl group.

[Formula 4]

In Formula (4), R ₈ and R ₉ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a carbon number It is a phenyl group which may be substituted with 1-6 alkyl groups. R ₁₀ is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted with an -O- group. In addition, some of the hydrogen atoms in the groups of R ₈ to R ₁₀ may be substituted with halogen atoms.

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

Light-shielding components such as black pigment, mixed color organic pigment, and light-shielding material, which are components (D) according to the present embodiment, have an average particle diameter of 1 to 1000 nm (measured by a laser diffraction/scattering method particle size distribution system or a dynamic light scattering method particle size distribution system) average particle diameter), a known light-shielding component can be used without particular limitation.

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

According to the function of the photosensitive resin composition made into the objective, the said (D)component may use only the 1 type independently, and may use 2 or more types together.

In addition, as an example of the organic pigment which can be used when using a mixed color organic pigment as component (D), the color index names include those of the following numbers, 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.

Among these, a black pigment is preferable and carbon black is more preferable.

The average primary particle diameter of carbon black is preferably 5 nm or more and 60 nm or less, more preferably 10 nm or more and 50 nm or less, and still more preferably 20 nm or more and 45 nm or less. In the present specification, the particle diameter or average primary particle diameter of the light-shielding component is the average value of the average value of the major axis and the minor axis obtained by observing the particles or primary particles of the light-shielding component with an electron microscope for 1500 light-shielding components. means The larger the average primary particle diameter of carbon black, the easier it is to disperse at a high concentration. By setting the average primary particle diameter of carbon black to a size that is not excessive, shape defects of secondary particles and decrease in surface roughness can be suppressed.

Moreover, it is preferable that the DBP oil absorption of carbon black is 100 ml/100 g or less. In addition, DBP oil absorption means the capacity of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS K 6217-4 (2017)). When the DBP oil absorption of carbon black is within the above range, the resistance value and blackness of the cured film can be made higher, and the decrease in applicability due to the high viscosity of the photosensitive resin composition can be suppressed.

Further, carbon black preferably has a pH of 2 or more and 10 or less, more preferably 5 or more and 9 or less, and still more preferably 4 or more and 8 or less. In addition, the pH value means a value obtained by measuring a mixture of carbon black and distilled water with a glass electrode pH meter. The higher the pH of the carbon black, the higher the stability of the carbon black. By setting the pH of the carbon black to a range in which it is not excessive, the adhesiveness of the cured film to the substrate can be further improved.

Moreover, it is preferable that carbon black has an ash content of 1.0% or less. When the ash content is 1.0% or less, the resistance value of the cured film can be further increased.

Moreover, it is preferable that the specific surface area of carbon black is 20 m<2>/g or more and 300 m<2>/g or less. When the specific surface area is 20 m 2 /g or more, the shape of the cured film is likely to be stable. Since the required amount of a dispersing agent, a dye, etc. can be reduced as a specific surface area is 300 m<2>/g or less, cost can be held down more.

Moreover, it is preferable that carbon black has an acidic functional group on the surface by oxidation treatment. In particular, it is preferable to have two or more types of acidic functional groups on the surface by plural types of oxidation treatment. The said acidic functional group can improve the dispersibility of carbon black. Examples of the oxidation treatment include treatment using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitrogen monoxide gas, nitrogen dioxide gas, anhydrous sulfuric acid, fluorine gas, concentrated sulfuric acid, various peroxides, and the like. Examples of the acidic functional group include a hydroxyl group, an oxo group, a hydroperoxy group, a carbonyl group, a carboxyl group, a peroxycarboxylic acid group, an aldehyde group, a ketone group, a nitro group, a nitroso group, an amide group, an imide group, a sulfonic acid group, a sulfinic acid group, A sulfenic acid group, a thiocarboxylic acid group, a chlorosyl group, a chloryl group, a perchloryl group, an iodosyl group, an iodyl group, and the like are included.

In addition, the surface of component (D) may be coated with a dye and subjected to surface treatment. In particular, carbon black whose surface is coated with a dye enhances the developability of the photosensitive resin composition, and also enhances the adhesion to the substrate, fine wire reproducibility, and light-shielding properties of a cured film formed by curing it, and can also increase the resistance value of the cured film. .

The dye may be one that can be adsorbed on the surface of the light-shielding component, and basic dyes, acid dyes, direct dyes, reactive dyes and the like can be used. In addition, at this time, when an acidic functional group is provided (oxidized) to the surface of the light-shielding component (particularly carbon black) in order to improve its dispersibility, an acidic dye (particularly a sulfonic acid group or a carboxyl group) easily interacting with the acidic functional group Acidic dyes having) are preferred. Moreover, compared with the dye which has an amino group etc. from a viewpoint of suppressing reaction with the acidic group which component (A) has, an acidic dye or a nonionic dye is preferable. Moreover, from a viewpoint of further improving the light-shielding property of a cured film, a dark color dye is preferable.

Specific examples of the dye include food coloring dyes such as Food Black No.1, Food Black No.2, Food Red No.40, Food Blue No.1, and Food Yellow No.7, Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X -34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, N.Y.), BASF Basacid Black SE 0228 (manufactured by BASF), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine (registered trademark) dyes (manufactured by Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (manufactured by Sandoz, Inc); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon), Direct Brilliant Pink B (manufactured by Crompton & Knowles), Carta Black 2GT (manufactured by Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz);, Pergasol Yellow CGP (manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazol Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; Berncolor A.Y. 34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc. Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix® dyes Dystar L.P. (Charlotte, NC), reactive dyes of various colors such as Procion Red H8B (Reactive Red 31) (manufactured by JCI America), Neozapon Red 492 (manufactured by BASF), Orasol Red G (manufactured by Ciba-Geigy) Manufacture), Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), Morfast Black Concentrate A (manufactured by Morton-Thiokol) Oil-soluble dyes such as the like are included. These may be used independently or may be used in combination of 2 or more types.

It is preferable that it is 0.5 mass % or more and 10 mass % or less with respect to the total mass in (D) component, and, as for content of the said dye, it is more preferable that it is 1 mass % or more and 7 mass % or less. The resistance value of a cured film can be raised, so that there are more quantities of dye. When the amount of the dye is not excessive, the thickening of the photosensitive resin composition due to the excess dye and the occurrence of aggregation caused by the excess dye impairing the dispersibility of other components can be suppressed.

In addition, the dye may be laked with a metal or metal salt. By laking the dye, it is possible to fix the dye to the surface of the light-shielding component via the metal or metal salt, and suppress the reduction in the above effect due to detachment of the dye from the surface of the light-shielding component. Examples of the metal include aluminum, magnesium, calcium, strontium, barium and manganese. Examples of the metal salts include hydrochlorides and sulfates of these metals. The content of the metal or metal salt is preferably 0.3 times mole or more, more preferably 0.5 times mole, and still more preferably 0.8 times mole relative to the amount of the dye.

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

The component (D) is usually mixed with other components as a light-shielding component dispersion dispersed in a solvent. In that case, a dispersant may be added. As the dispersant, known compounds used for dispersing the pigment (light-shielding component) (compounds commercially available under names such as dispersing agent, dispersing wetting agent, and dispersing accelerator) and the like can be used without particular limitation.

Examples of the dispersing agent include cationic polymer-based dispersing agents, anionic polymer-based dispersing agents, nonionic polymer-based dispersing agents, and pigment derivative type dispersing agents (dispersion aids). 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 for the colorant, and has an amine value of 1 to 100 mgKOH/g, It is preferable that it is a cationic polymer system dispersing agent in the range of 1000-100000 number average molecular weight (Mn). It is preferable that it is 1-35 mass parts with respect to the light-shielding component, and, as for the compounding quantity of this dispersing agent, it is more preferable that it is 2-25 mass parts. In addition, high-viscosity substances such as resins generally have an action of stabilizing dispersion, but substances that do not have dispersion-accelerating ability are not treated as dispersants. However, use for the purpose of stabilizing dispersion is not limited.

As the fine particles of component (E), aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, sodium metasilicate and the like can be used. Among these, aluminum oxide fine particles are preferable. While the refractive index of a transparent substrate such as glass is about 1.5, since the refractive index of carbon black serving as a light-shielding component is about 2.0, by using fine particles having a lower refractive index than the refractive index of the light-shielding component, the refractive index of the cured film containing the fine particles can be lowered. The refractive index of the fine particles as component (E) is preferably from 1.50 to 1.80, and more preferably from 1.55 to 1.75. The refractive index of the aluminum oxide fine particles is 1.74 (literature value), and since the refractive index is located near the middle of the transparent substrate and the light-shielding component, it is thought that using the fine particles reduces the difference in refractive index between the glass and the cured film and reduces the reflectance. . In addition, many of the particles having a large refractive index such as component (E) have a large specific gravity, and are likely to be unevenly distributed near the interface between the transparent substrate and the cured film when the photosensitive resin composition is applied on the substrate. Therefore, component (E), even in a small amount, can sufficiently reduce the difference in refractive index between the base material and the cured film and suppress reflection. Moreover, by making component (E) small, the relative content of component (D) can be raised and the optical density of a cured film can be raised. It is thought that (E) component can make high light-shielding property and low reflectance of a cured film compatible by these actions. Furthermore, by using a small amount of component (E), it is possible to make it difficult to produce jagged edges of the pattern due to component (E).

The aluminum oxide particles used in the present invention are produced by a gas phase reaction or a liquid phase reaction, and the shape (spherical or non-spherical) is not particularly limited.

The average particle diameter of component (E) is preferably 10 to 300 nm, more preferably 50 to 250 nm, and still more preferably 55 to 250 nm. If the average particle diameter of the particles is 10 nm or more, the particle diameter is sufficiently large and the weight of the particles is large, so that they are easily distributed in the vicinity of the interface between the transparent substrate and the cured film, so that the effect of reducing reflectance can be sufficiently obtained. In addition, if the average particle size of the particles is 300 nm or less, jagged edges of the pattern are less likely to occur. In addition, an average particle diameter is an average primary particle diameter when component (E) consists of primary particles, and an average secondary particle diameter when component (E) consists of secondary particles.

(E) About the compounding ratio of component, it is preferable that it is 1-30 mass % with respect to solid content in the photosensitive resin composition, and it is more preferable that it is 2-10 mass %. (E) When content of component is 1 mass % or more, the refractive index of a cured film is fully raised, and the reflectance reduction effect becomes high. (E) When content of component is 30 mass % or less, high-definition pattern formation becomes possible.

It is preferable that it is 85/15 - 99/1, and, as for the compounding ratio of component (D) and (E) component, it is more preferable that it is 92/8 - 98/2 in weight ratio (D)/(E). (D) By making the compounding ratio of component 85/15 or more, the light-shielding property of a cured film can be further improved. Moreover, by reducing the relative amount of the component (E), it is possible to make it difficult to produce jagged edges of the pattern edge portion due to the component (E). In addition, even if the relative amount of component (E) is reduced to the above level, the effect of reducing reflectance by component (E) is sufficiently exhibited.

It is preferable to use the solvent which is (F) component other than the component (A)-(E) for the photosensitive resin composition of this invention. 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, Methyl Carbitol, Ethyl Carbitol, Butyl Carbitol, 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, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Acetic acid esters of are included. A uniform solution-like composition can be obtained by dissolving and mixing these individually or in combination of two or more types.

Moreover, in the photosensitive resin composition of this invention, as needed, resins other than (A) component, such as an epoxy resin, a hardening|curing agent, a hardening accelerator, a thermal polymerization inhibitor, antioxidant, a plasticizer, and a filler other than microparticles|fine-particles with a refractive index of 1.50 or more and 1.80 or less , a leveling agent, an antifoaming agent, a surfactant, and additives such as a coupling agent can be blended.

Examples of the thermal polymerization inhibitor and 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, and the like. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltriethoxysilane and the like. included

The photosensitive resin composition of the present invention contains an unsaturated group-containing photosensitive resin as component (A) and at least two or more components as component (B) in a solid content (solid content includes a photopolymerizable compound that becomes a solid content after curing) excluding a solvent. A photopolymerizable compound having an unsaturated bond, a photopolymerization initiator as component (C), at least one light-shielding component selected from black pigment, mixed color pigment and light-shielding material as component (D), and (E) a refractive index of 1.50 or more and 1.80 or less It is preferable that the fine particles of are contained at 80 mass% or more in total, and it is more preferable that they are contained at 90 mass% or more. Although the amount of the solvent changes depending on the target viscosity, it is preferably 40 to 90% by mass with respect to the total amount.

Further, the cured film formed by curing the photosensitive resin composition of the present invention is cured by, for example, applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent, and irradiating light (including ultraviolet rays, radiation, etc.) is obtained A desired pattern is obtained by using a photomask or the like to form a portion that is exposed to light and a portion that is not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkali solution.

In the cured film formed by curing the photosensitive resin composition of the present invention, the light-shielding degree OD [μm ^-1 ] of the cured film having a film thickness of 1 μm is preferably 2.6 or more, more preferably 3.0 or more, still more preferably 3.3 or more. . Moreover, it is preferable that reflectance is 6.5 % or less, and, as for the cured film formed by hardening|curing the photosensitive resin composition of this invention, it is more preferable that it is 5.0 % or less. Moreover, the value obtained by dividing the reflectance [%] by the light-shielding degree OD [μm ^-1 ] of the cured film obtained by curing the photosensitive resin composition of the present invention is preferably less than 1.65, and more preferably less than 1.50. By suppressing the reflectance in the light-shielding region where the light-shielding degree OD [μm ^-1 ] of the cured film having a film thickness of 1 μm is higher, it is possible to obtain a display device having a cured film (light-shielding film) excellent in visibility as a black matrix.

In particular, the cured film obtained by curing the photosensitive resin composition of the present invention has a cured film having a film thickness of 1 μm, in which the light-shielding degree OD [μm ^-1 ] is 2.6 or more, and the value obtained by dividing the reflectance [%] by the light-shielding degree OD is less than 1.65. Further, the reflectance is 6.5% or less, and preferably the cured film having a film thickness of 1 μm has a light-shielding degree OD [μm ^-1 ] of 3.0 or more, and a value obtained by dividing the reflectance [%] by the light-shielding degree OD is less than 1.50; In addition, the reflectance is 5.0% or less, more preferably, the light-shielding degree OD [μm ^-1 ] of a cured film having a film thickness of 1 μm is 3.3 or more, and the value obtained by dividing the reflectance [%] by the light-shielding degree OD is less than 1.50, and The reflectance is used in the range of 5.0% or less.

In addition, for a color filter or touch panel having a cured film (light shielding film) of the present invention as a black matrix, for example, a cured film having a film thickness of 1.0 to 2.0 μm is formed on a transparent substrate, and after forming the light shielding film, red and blue colors are formed. and forming each green pixel by photolithography, and injecting red, blue, and green ink into the light-shielding film by an inkjet process.

Moreover, the cured film formed by hardening the photosensitive resin composition of this invention can also be used as a black column spacer of a liquid crystal display device. For example, a plurality of portions having different film thicknesses may be produced using a single black resist, one functioning as a spacer, and the other functioning as a black matrix.

About each process of the film-forming method of the cured film by application|coating and drying of the photosensitive resin composition, it illustrates concretely.

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

As the radiation used for exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. can be used, but the range of the wavelength of the radiation is preferably 250 to 450 nm. Moreover, as a developing solution suitable for this alkali development, aqueous solutions, such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide, can be used, for example. Although these developing solutions may be appropriately selected according to the characteristics of the resin layer, it is also effective to add a surfactant as necessary. The developing temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing device, ultrasonic cleaner, or the like. 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 puddle (liquid mounting) developing method, or the like can be applied.

After development in this way, 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. This is carried out by heating with an oven, hot plate or the like, similarly to prebaking. The patterned cured film (light-shielding film) of the present invention is formed through each step by the photolithography method. Then, polymerization or curing (the combination of both is sometimes referred to as curing) is completed by heat, and a light-shielding film having a desired pattern can be obtained. The curing temperature at this time is preferably 160 to 250°C.

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

The photosensitive resin composition of the present invention can be suitably used as a coating material. In particular, ink for color filters used in liquid crystal display devices or imaging elements, and light-shielding films formed therefrom are useful as color filters, liquid crystal projections, black matrices for touch panels, and the like. In addition, the photosensitive resin composition of the present invention can be used in various multi-color displays such as organic electroluminescent devices represented by organic EL elements, color liquid crystal displays, color facsimiles, and image sensors, in addition to color filter inks for color liquid crystal displays. It can also be used as an ink material for color separation or light blocking. According to the color filter of the present invention, the reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate and the reflection of light emission from the element when used in, for example, an organic EL element can be reduced. there is. In short, it is possible to realize improvement in bright spot contrast by reducing reflection of external light and improvement in luminous efficiency by improving 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, the synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin as component (A) is described, but the evaluation of the resin in these synthesis examples was performed as follows unless otherwise noted.

[solid content concentration]

1 g of the resin solution obtained in Synthesis Example was impregnated with a glass filter [Weight: W0 (g)], weighed [W1 (g)], and obtained from the weight [W2 (g)] after heating at 160 ° C. for 2 hours by the following formula did

Solid content concentration (% by weight) = 100 × (W2 - W0) / (W1 - W0)

[acid value]

The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to obtain the resultant.

[Molecular Weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) piece) + TSKgelSuper H-5000 (1 piece) (manufactured by Tosoh Corporation, temperature: 40 ° C., speed: 0.6 ml / min), and as a standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) conversion value as a weight average The molecular weight (Mw) was determined.

[Average Particle Size]

The average particle diameter of the aluminum oxide particles was determined by the cumulant method using a dynamic light scattering particle size distribution analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

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

BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. An epoxy compound in which X is a fluorene-9,9-diyl group, R ₁ to R ₄ are hydrogen, and l is 0 to 0.15 in the compound of the general formula (1).

DCPMA: dicyclopentanyl methacrylate

GMA: Glycidyl methacrylate

St: Styrene

AA: acrylic acid

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

THPA: tetrahydrophthalic anhydride

SA: succinic anhydride

TEAB: tetraethylammonium bromide

AIBN: Azobisisobutyronitrile

TDMAMP: Trisdimethylaminomethylphenol

HQ: Hydroquinone

TEA: triethylamine

TPGDA: tripropylene glycol diacrylate

PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example A1]

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

[Synthesis Example A2]

In a 1 L four-neck flask equipped with a reflux condenser, PGMEA (300 g) was placed, and the inside of the flask was purged with nitrogen, and then the temperature was raised to 120°C. Next, a mixture of monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol), and AIBN (10 g) dissolved in a flask) was placed in a dropping funnel for 2 hours. It was dripped over and stirred at 120 degreeC for 2 hours, and the copolymer solution was obtained.

Next, after purging the inside of the flask with air, AA (24.0 g, 0.33 mol (95% of the number of moles of GMA added)), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and 120 It stirred at degreeC for 6 hours, and obtained the copolymer solution containing a polymerizable unsaturated group. SA (30.0 g, 90% of the number of moles of AA added) and TEA (0.5 g) were added to the resulting polymerizable unsaturated group-containing copolymer solution, followed by reaction at 120°C for 4 hours, and unsaturated group-containing alkali-soluble resin (A)-2 got The solid content concentration of the resin solution was 46.0 mass %, the acid value (solid content conversion) was 76 mgKOH/g, and the Mw by GPC analysis was 5300.

In addition, carbon black whose surface was coated with a dye was prepared by the following method.

[Preparation Example D1]

1000 g of carbon black (TPX-1099: manufactured by Cabot) was mixed with water to prepare 10 L of slurry, stirred at 95°C for 1 hour, allowed to cool, and washed with water. This was mixed with water again to prepare 10 L of slurry, 42.9 g of 70% nitric acid was added, and the mixture was stirred at 40°C for 4 hours. After standing to cool and washing with water, it mixed with water again, prepared 10 L of slurries, added 769.2 g of 13% sodium hypochlorite aqueous solution, and stirred at 40 degreeC for 6 hours. After standing to cool and washing with water, it was mixed with water again to prepare 10 L of slurry, 38.1 g of a dye (Direct Deep BLACK) having a purity of 38.4% was added, stirred at 40 ° C. for 1 hour, and then 10.1 g of aluminum sulfate was further added. It was added and stirred at 40 degreeC for 1 hour. After cooling this, it was washed with water and dried by filtration to obtain dye-coated carbon black.

The above dye-coated carbon black, a polymer dispersant, a dispersing resin (alkali-soluble resin ((A)-1) of Synthesis Example A1), and PGMEA were mixed and dispersed with a bead mill so that the concentration of the dye-coated carbon black was 25.0 mass. %, a carbon black dispersion (D)-1 having a concentration of 2.0% by mass of the polymer dispersant and a concentration of 8.0% by mass of the dispersion resin was obtained.

The photosensitive resin composition of Examples 1-7 and Comparative Examples 1-3 was prepared with the compounding quantity (unit is a mass part) of Table 1. The compounding components used in Table 1 are as follows.

(Alkali-soluble resin containing polymerizable unsaturated group)

(A)-1: Alkali-soluble resin solution obtained in Synthesis Example A1 (solid content concentration: 56.1% by mass)

(A)-2: Alkali-soluble resin solution obtained in Synthesis Example A2 (solid content concentration: 46.0% by mass)

(photopolymerizable compound)

(B): A mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent weight: 96 to 115), manufactured by Nippon Kayaku Co., Ltd.)

(photopolymerization initiator)

(C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (Irgacure OXE-02, Manufactured by BASF Japan, "Irgacure" is a registered trademark of the company)

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

(carbon black dispersion)

(D)-1: 25% by mass of dye-coated carbon black obtained in Preparation Example D1, 2% by mass of polymer dispersant, and 8% by mass of dispersion resin (alkali-soluble resin ((A)-1) of Synthesis Example A1) concentration Pigment dispersion in PGMEA solvent (solid content: 35% by mass)

(D)-2: 25 mass% carbon black concentration, 3 mass% polymer dispersant concentration, dispersion resin (alkali-soluble resin of Synthesis Example A1 ((A)-1)) 5 mass% PGMEA solvent pigment dispersion (solid content) 33% by mass)

(E)-1: Aluminum oxide TPGDA dispersion "ALTPGDA 30 WT%-A03" (manufactured by CIK Nanotech Co., Ltd., aluminum oxide concentration 30 mass%, TPGDA concentration 70 mass%, average particle size 90 nm)

(E)-2: aluminum oxide TPGDA dispersion "ALTPGDA 25 WT%-A07" (manufactured by CIK Nanotech Co., Ltd., aluminum oxide concentration 25 mass%, TPGDA concentration 75 mass%, average particle size 50 nm)

(E)-3: Silica PGMEA dispersion "YA050C" (manufactured by Admatex Co., Ltd., silica concentration 30 mass%, PGMEA concentration 70 mass%, average particle size 50 nm)

(solvent)

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

(F)-2: cyclohexanone (ANON)

(Other components) -1:3-isocyanate propyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(Other components)-2: 1% by mass ANON diluted solution of aralkyl-modified polymethylalkylsiloxane (BYK-323, manufactured by Big Chemie Japan Co., Ltd.)

[evaluation]

A cured film (light-shielding film) formed by curing the photosensitive resin composition for use in evaluation was produced as follows.

(Preparation of Cured Film (Coating Film) for Optical Density (OD) Evaluation)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet light having a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 with a low-pressure mercury lamp, and the surface thereof was washed. Glass substrate of 125 mm × 125 mm “#1737” (manufactured by Corning Co., Ltd.) (hereinafter (referred to as "glass substrate"), apply using a spin coater so that the film thickness after heat curing treatment is 1.2 μm, and prebake at 90 ° C. for 1 minute using a hot plate to prepare a cured film (coating film) did A photocuring reaction was performed by irradiating with 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 the negative photomask.

Then, the exposed cured film (light-shielding film) was subjected to development treatment at 25°C with a 0.05% potassium hydroxide solution at a shower pressure of 1 kgf/cm 2 for 20 seconds from the development time at which a pattern began to appear (break time = BT). After carrying out, spray washing was performed at 5 kgf/cm 2 to remove 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, this It cured (post-bake) to obtain cured films (light-shielding films) according to Examples 1 to 7 and Comparative Examples 1 to 3.

[Measurement of film thickness]

(Assessment Methods)

Using a step meter ("Tencor P-17" manufactured by KLA-Tencor), the step difference between the surface of the glass substrate and the surface of the cured film was measured under the conditions of a measurement range of 500 µm, a scanning speed of 50 µm/sec, and a sampling rate of 20 Hz. It was measured, and the average value was made into the average thickness of the cured film.

[Optical Density (OD) Evaluation]

(Assessment Methods)

The optical density (OD) was measured using a transmission densitometer "X-rite 361T (V)" manufactured by X-rite. The optical density (OD) per 1 μm of film thickness was calculated from the above measured film thickness and optical density (OD).

The optical density (OD) was calculated from the following formula (5).

Optical Density (OD) = -log ₁₀ T Equation (5)

(T represents transmittance)

[Evaluation of reflectance]

(Assessment Methods)

With respect to a substrate with a cured film (light-shielding film) prepared in the same way as the cured film (light-shielding film) for optical density (OD) evaluation, using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Sciences Co., Ltd.), Each reflectance of the cured film (light shielding film) side and the substrate (glass substrate) side was measured under conditions of a C light source, an incident angle of 2°, and a wavelength range of 380 to 780 nm.

(Preparation of cured film (light shielding film) for evaluation of development characteristics)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet light having a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 with a low-pressure mercury lamp, and the surface thereof was washed. Glass substrate of 125 mm × 125 mm “#1737” (manufactured by Corning Co., Ltd.) (hereinafter (referred to as "glass substrate"), apply using a spin coater so that the film thickness after heat curing treatment is 1.2 μm, and prebake at 90 ° C. for 1 minute using a hot plate to prepare a cured film (light shielding film) did Next, the exposure gap was adjusted to 100 μm, and a negative photomask with line/space = 10 μm/50 μm was covered on the dry cured film, and an ultraviolet ray of 50 mJ/cm 2 was applied with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 . was irradiated to perform a photocuring reaction of the photosensitive portion.

Subsequently, the exposed cured film (light-shielding film) was subjected to development treatment at 25° C. with a 0.04% potassium hydroxide solution at a shower pressure of 1 kgf/cm 2 for +20 seconds from the development time at which patterns began to appear (break time = BT). After that, spray washing with 5 kgf/cm 2 is performed, the unexposed portion of the cured film (light shielding film) is removed to form a cured film pattern on the glass substrate, and the cured film is cured at 230° C. for 30 minutes using a hot air dryer (Post-baking) to obtain cured films (light-shielding films) according to Examples 1 to 7 and Comparative Examples 1 to 3.

The cured films (light-shielding films) formed by curing the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 obtained above were evaluated for the following items.

[Evaluation of development characteristics]

(pattern linearity)

(Assessment Methods)

A 10 μm mask pattern of the main curing (postbake) was observed using an optical microscope. In addition, evaluation of pattern linearity was performed in the case of BT+20 second. In addition, △ or more was set as pass.

(Evaluation Criteria for Development Characteristics)

○: Less than 1% of projections of 0.5 μm are observed with respect to a line width of 10 μm when the pattern length is 100%, and the jagged pattern of the pattern edge portion is confirmed.

△: The jagged pattern at the edge of the pattern is confirmed at a rate of 1% or more and less than 25% of projections of 0.5 μm with respect to a line width of 10 μm, when the length of the pattern is 100%.

×: When the pattern edge portion has a serration pattern, when the length of the pattern is 100%, a projection of 0.5 μm is observed at a rate of 25% or more with respect to a line width of 10 μm.

Table 2 shows the evaluation results.

In the photosensitive resin composition of Examples 1-7, it was confirmed that the reflectance from the board|substrate side could be reduced in high light-shielding factor compared with the system using a silica particle (Comparative Examples 1-3). Moreover, it was confirmed that all cured films (light-shielding films) obtained by curing the photosensitive resin compositions of Examples 1 to 3 and 5 had good pattern linearity.

ADVANTAGE OF THE INVENTION According to the photosensitive resin composition of this invention, the photosensitive resin composition which has both high light-shielding property and low reflectance, a cured film using the same, a color filter, and a touch panel can be provided. Moreover, according to this color filter and a touchscreen, various display devices excellent in visibility can be provided.

Claims (9)

(A) an alkali-soluble resin containing an unsaturated group;
(B) a photopolymerizable compound having at least two unsaturated bonds;
(C) a photopolymerization initiator;
(D) at least one light-shielding component selected from the group consisting of black pigments, mixed-color pigments, and light-shielding materials;
(E) A photosensitive resin composition containing fine particles having a refractive index of 1.50 to 1.80. According to claim 1,
The (E) fine particles are aluminum oxide particles, the photosensitive resin composition. According to claim 1,
The photosensitive resin composition in which the average particle diameter of the said (E) microparticles|fine-particles is 10-300 nm. According to claim 1,
The photosensitive resin composition whose ratio in solid content of said (E) microparticles|fine-particles is 1-30 mass %. According to claim 1,
The light-shielding degree OD [μm ^-1 ] of a cured film having a film thickness of 1 µm obtained by curing the photosensitive resin composition with light is 2.6 or more, and the reflectance [%] of the cured film is 6.5 or less, and the reflectance of the cured film is as described above. The photosensitive resin composition in which the value divided by light-shielding degree OD is less than 1.65. A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 5. The color filter which has the cured film of Claim 6 as a black matrix. The touch panel which has the cured film of Claim 6 as a black matrix. A display device comprising the color filter according to claim 7 or the touch panel according to claim 8.