Photosensitive resin composition for black resist, light-blocking film, color filter, touch panel, and display device

Abstract

The present invention relates to a photosensitive resin composition for black resist, light shielding film, color filter, touch panel, and display device. The present invention provides a photosensitive resin composition for black resist, which has high light shielding property and low reflectance and can suppress generation of agglomerates. The photosensitive resin composition for black resist of the present invention comprises: (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least 2 or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light shielding component selected from the group consisting of a black pigment, a mixed color pigment, and a light shielding material, (E) a silicon oxide particle, and (F) a solvent.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition for a black resist, a light-shielding film cured from the photosensitive resin composition, a color filter having the light-shielding film, a touch panel, and a display device having the color filter and the touch panel. Background Technology

[0002] In recent years, due to the booming development of mobile terminals, display devices such as touch panels and LCD panels used outdoors or in vehicles have increased. In the above-mentioned display devices, in order to block light leakage from the periphery of the back LCD panel, a light-shielding film is provided on the outer frame of the touch panel. In addition, in order to suppress light leakage from the screen when displaying black and to suppress color mixing between adjacent color resists, a black matrix is ​​provided on the LCD panel.

[0003] In display devices and the like, to suppress light leakage and improve screen visibility, the concentration of black pigment in the light-shielding film is increased to enhance its light-shielding properties (reduce light transmittance). However, black pigment has a higher refractive index than the transparent substrate or curable resin. Therefore, increasing the concentration of black pigment in the light-shielding film may lead to increased reflectivity when viewed from the side opposite to the transparent substrate where the light-shielding film is formed. Consequently, increased reflection at the interface between the light-shielding film and the transparent substrate results in reflections on the light-shielding film and noticeable black matrix boundaries due to differences in reflectivity with the color filter's colored portion.

[0004] Therefore, there is a need for a photosensitive resin composition for a black resist that has both high light-blocking properties and low reflectivity, a light-blocking film formed therefrom by curing, and a color filter.

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition comprising hydrophobic silica particles and a specific dispersant (ethyl carbamate-based dispersant). According to Patent Document 1, by using the hydrophobic silica particles and the specific dispersant, a black matrix with both high opacity and low reflectivity can be formed.

[0006] [Existing technical documents]

[0007] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2015-161815. Summary of the Invention

[0009] [The problem the invention aims to solve]

[0010] However, upon review, the inventors of this application discovered that the black photosensitive resin composition described in Patent Document 1 could not produce a light-shielding film that combined both the desired light-shielding properties and reflectivity. Furthermore, the black photosensitive resin composition described in Patent Document 1 produces aggregates derived from silicon oxide particles, which could potentially cause light leakage in the thicker lines and outer frame, as well as foreign matter in the openings.

[0011] Therefore, the inventors of this application, after careful examination to solve the problems in previous photosensitive resin compositions, discovered that silica particles have the characteristic of easily agglomerating due to the silanol groups present on the particle surface. Generally, they can be dispersed in organic solvents by coating with a silane coupling agent. However, it is not easy to coat all the silanol groups present on the surface with a silane coupling agent, and when mixed with resin compositions of different polarities, the dispersion becomes unstable and tends to agglomerate. It was found that by mixing a polar solvent with a high relative permittivity as an inhibitor solvent within an appropriate range, the silanol groups on the surface of the silica particles are stabilized through solvation, thereby suppressing the agglomeration of silica particles.

[0012] The present invention was made in view of this point, with the aim of providing a photosensitive resin composition for a black resist having high light-blocking properties and low reflectivity and suppressing the formation of agglomerates, a light-blocking film formed by curing the photosensitive resin composition, a color filter and a touch panel having the light-blocking film, and a display device having the color filter and the touch panel.

[0013] [Methods for solving the problem]

[0014] The photosensitive resin composition for black resist of the present invention comprises the following components as essential components: (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-blocking component selected from black pigments, mixed pigments and light-blocking materials, (E) silica particles, and (F) a solvent; wherein the aforementioned solvent (F) comprises: a first solvent being propylene glycol monomethyl ether acetate, and a second solvent having a relative permittivity of 10 to 30 at 23°C; the aforementioned solvent (F) as a whole has a relative permittivity of 8.5 or more at 23°C.

[0015] The light-shielding film of the present invention is a light-shielding film formed by curing the above-mentioned black resist with a photosensitive resin composition.

[0016] The color filter of the present invention has the above-mentioned light-shielding film as a black matrix.

[0017] The touch panel of the present invention has the above-mentioned light-shielding film as a black matrix.

[0018] The display device of the present invention has the above-described color filter or the above-described touch panel.

[0019] [The effects of the invention]

[0020] According to the present invention, a photosensitive resin composition for a black resist having high light-blocking properties and low reflectivity and suppressing the formation of agglomerates can be provided, as well as a light-blocking film formed by curing the photosensitive resin composition, a color filter and a touch panel having the light-blocking film, and a display device having the color filter and the touch panel. Detailed Implementation

[0021] The present invention will now be described in detail. The photosensitive resin composition for black resists of the present invention (hereinafter referred to as the photosensitive resin composition) comprises the following essential components: (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-blocking component selected from black pigments, mixed pigments, and light-blocking materials, (E) silica particles, and (F) a solvent. Components (A) to (F) will be described below.

[0022] 1.(A)Ingredients

[0023] The photosensitive resin containing unsaturated groups belonging to component (A) of this embodiment is preferably one that 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. The resin described above is not particularly limited and can be widely used.

[0024] Examples of the above-mentioned photosensitive resins containing unsaturated groups include adducts of epoxy (meth)acrylate acids obtained in the following manner: an epoxide having two glycidyl ether groups derived from bisphenols (hereinafter also referred to as "bisphenol-type epoxides represented by general formula (1)") is reacted with (meth)acrylate, and the resulting compound having hydroxyl groups is then reacted with a polycarboxylic acid or its anhydride. Epoxides derived from bisphenols refer to epoxides obtained by reacting bisphenols with epihaloalcohols or their equivalents. Furthermore, "(meth)acrylate" is a general term for acrylic acid and methacrylic acid, referring to one or both of these.

[0025] The photosensitive resin containing unsaturated groups belonging to component (A) is more preferably: a photosensitive resin containing unsaturated groups obtained by further reacting a bisphenol-derived epoxide having two glycidyl ether groups, represented by general formula (1), with (meth)acrylic acid and a polycarboxylic acid or its anhydride.

[0026] General formula (1)

[0027] (In formula (1), R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl atom with 1 to 5 carbon atoms or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond represented by general formula (2), and l is an integer from 0 to 10).

[0028] General formula (2)

[0029] The bisphenol type epoxide represented by general formula (1) is an epoxide with two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction is generally accompanied by oligomerization of diglycidyl ether compounds, and therefore also includes epoxides with more than two bisphenol skeletons.

[0030] Examples of bisphenols used in this reaction include: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichloro ... 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-dimethyl)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'-bisphenol, 3,3'-bisphenol, etc. Among these, bisphenols containing fluorene-9,9-diyl groups are preferred.

[0031] Furthermore, examples of monoanhydrides of (a) dicarboxylic acids or tricarboxylic acids that react with the hydroxyl groups in an epoxy (meth)acrylate molecule to react with such an epoxide with (meth)acrylic acid include: monoanhydrides of chain-type dicarboxylic acids or tricarboxylic acids, monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids, etc. Examples of monoanhydrides of chain-type dicarboxylic acids or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxyglutaric acid, pimelic acid, sebacic acid, octanoic acid, diglycollic acid, etc. Further examples include monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituents. Furthermore, examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include: cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornenedicarboxylic acid. Further, examples also include monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituents. Additionally, examples of monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include: phthalic acid, isophthalic acid, and trimellitic acid. Further, examples also include monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituents.

[0032] Furthermore, the dianhydride of (b) tetracarboxylic acids reacting with epoxy (meth)acrylates is an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, or an aromatic tetracarboxylic acid. Examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc. Further examples include acid dianhydrides of tetracarboxylic acids with any substituents. Examples of acid dianhydrides of alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norcamphenetetracarboxylic acid, etc. Further examples include acid dianhydrides of tetracarboxylic acids with any substituents. Examples of acid dianhydrides of aromatic tetracarboxylic acids include pyromellitic acid, diphenyl ketone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, etc. Further examples include acid dianhydrides of tetracarboxylic acids with any substituents.

[0033] The molar ratio (a) / (b) of the anhydride of (a) dicarboxylic acid or tricarboxylic acid reacting with epoxy (meth)acrylate to the dianhydride of (b) tetracarboxylic acid is preferably from 0.01 to 10.0, more preferably from 0.02 or more but not exceeding 3.0. When the molar ratio (a) / (b) deviates from the above range, the optimal molecular weight for forming a photosensitive resin composition with good patterning properties cannot be obtained, and therefore it is not preferred. In addition, the smaller the molar ratio (a) / (b), the larger the molecular weight becomes, and the alkali solubility tends to decrease.

[0034] Furthermore, the reaction of the epoxide with (meth)acrylic acid, and the reaction of the resulting epoxy (meth)acrylate with polycarboxylic acids or their anhydrides, are not particularly limited, and well-known methods can be used. Additionally, the weight-average molecular weight (Mw) of the photosensitive resin containing unsaturated groups synthesized in the above reaction is preferably 2000 to 10000, and the acid value is preferably 30 to 200 mg KOH / g.

[0035] Other preferred examples of photosensitive resins containing unsaturated groups as component (A) include copolymers of (meth)acrylic acid, (meth)acrylates, etc., which are resins having (meth)acryloyl and carboxyl groups. Examples of the above-mentioned resins include alkali-soluble resins containing polymerizable unsaturated groups obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting it with an anhydride of a dicarboxylic acid or tricarboxylic acid. The copolymers mentioned above can be referenced to the copolymer shown in Japanese Patent Application Publication No. 2014-111722, which is composed of 20 to 90 mol% repeating units of dieter gylcerol derived from end-hydroxyl groups esterified via (meth)acrylic acid, and 10 to 80 mol% repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized therewith, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g; and the alkali-soluble resin containing polymerizable unsaturated groups shown in Japanese Patent Application Publication No. 2018-141968, which is a polymer comprising units derived from (meth)acrylate compounds and units having (meth)acryloyl groups and di or tricarboxylic acid residues, having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mgKOH / g.

[0036] Regarding component (A), the photosensitive resin containing unsaturated groups may be used alone or in combination with two or more.

[0037] 2. (B) Component

[0038] Examples of photopolymerizable monomers having at least two or more unsaturated bonds in component (B) of this embodiment include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. The monomers include (meth)acrylates such as pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxy-modified hexa(meth)acrylate, caprolactone-modified pentaerythritol hexa(meth)acrylate, and dendritic polymers containing (meth)acrylate groups, which are compounds having vinyl double bonds. These monomers can be used individually or in combination of two or more. Furthermore, the photopolymerizable monomer having at least two vinyl unsaturated bonds is preferably capable of crosslinking molecules containing alkali-soluble resins; to achieve this function, it is more preferable to use monomers having three or more unsaturated bonds. Furthermore, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acrylic acid groups in one molecule is preferably 50 to 300 g / eq, and more preferably 80 to 200 g / eq. Additionally, component (B) does not have free carboxyl groups.

[0039] A dendritic polymer having a (meth)acrylyl group is a compound with unsaturated bonds that can be contained in the composition as component (B). Examples of such a dendritic polymer include dendritic polymers obtained by adding a partial carbon-carbon double bond of a (meth)acrylyl group to a polyfunctional (meth)acrylate with a multi-thiol compound. Specifically, this includes dendritic polymers obtained by reacting the (meth)acrylyl group of a polyfunctional (meth)acrylate represented by general formula (3) with a multi-thiol compound represented by general formula (4).

[0040] General formula (3)

[0041] (In formula (3), R5 is a hydrogen atom or a methyl group, and R6 is a group of R7(OH) atoms.) kR7 is the residue remaining after n hydroxyl groups from the k hydroxyl groups in the formula are supplied to the ester bonds. R7 is the residue remaining after removing the hydroxyl groups from the polyol, polyol ether, or ester of polyol ether and hydroxy acid. Preferred R7(OH)k is a polyol based on a non-aromatic straight-chain or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyol ether formed by the dehydration condensation of multiple molecules of the polyol and the linkage by ether bonds, or an ester of these polyols or polyol ethers with hydroxy acid. k and n independently represent integers from 2 to 20, but k ≥ n.

[0042] General formula (4)

[0043] (In formula (4), R8 is a single bond or a hydrocarbon group with 1 to 6 carbon atoms and 2 to 6 valences, and m is 2 when R8 is a single bond and has the same valence as R8 when R8 is a group with 2 to 6 valences.)

[0044] Examples of polyfunctional (meth)acrylates represented by general formula (3) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, etc. These compounds may be used alone or in combination with two or more.

[0045] Examples of polythiol compounds represented by general formula (4) include: trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thioglycolate), pentaerythritol tetras (thioglycolate), pentaerythritol tris (thioglycolate), pentaerythritol tetras (thioglycolate), dipentaerythritol hexas (thioglycolate), dipentaerythritol hexas (thioglycolate), etc. These compounds may be used alone or in combination of two or more.

[0046] The mixing ratio of component (A) to component (B), by weight (A) / (B), is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20. When the mixing ratio of component (A) is 30 / 70 or higher, the cured product after photocuring is less likely to become brittle. In addition, the acid value of the coating in the unexposed area is less likely to decrease, thus suppressing the decrease in solubility in alkaline developer. Accordingly, the defect of jagged pattern edges that cannot be sharpened is less likely to occur. In addition, when the mixing ratio of component (A) is 90 / 10 or lower, the proportion of photoreactive functional groups in the resin is sufficient, thus forming the desired cross-linked structure. Furthermore, the acid value in the resin component is not too high, so the solubility of the exposed area in alkaline developer is less likely to increase, thus suppressing the formation of a pattern that is thinner than the target line width or pattern defects.

[0047] 3. (C) Component

[0048] Examples of photopolymerization initiators (C) in this embodiment include: acetophenones, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropionylphenyl, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and other acetophenone derivatives; diphenyl ketones, 2-chlorodiphenyl ketone, p,p'-bis(dimethylaminodiphenyl ketone), and other diphenyl ketone derivatives; benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin ether derivatives; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, and other biimidazole compounds; 2-trichloromethyl-5-styryl-1,3,4- diazole, 2-trichloromethyl-5-(p-cyanostyl)-1,3,4- diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halogenated methylthiazole compounds such as diazoles; 2,4,6-trichloromethyl)-1,3,5-trichloromethyl 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-trimethyl 2-Phenylacet-4,6-bis(trichloromethyl)-1,3,5-tris(2, ... 2-(4-Chlorophenyl)-4,6-bis(trichloromethyl-1,3,5-trichlorophenyl) 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(trichloromethyl ... 2-(4-Methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri 2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxystyryl) 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-tris(methylthiostyryl) isohalomethyl-S-tri Class of compounds; acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylhydrothiophenyl)but-1,2-dione-2-oxime-O-benzoate, 1-(4-methylhydrothiophenyl)but-1,2-dione-2-oxime-O-acetate, 1-(4-methylhydrothiophenyl)but-1-one-oxime-O-acetate, 4-ethoxy-2 O-acyl oxime compounds such as methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyl oxime; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; and 2-mercaptobenzimidazole, 2-mercaptobenzo[…]. Thiol compounds such as azoles and 2-mercaptobenzothiazoles, and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators can be used alone or in combination of two or more.

[0049] Examples of O-acyloxime compounds that are preferred for use include O-acyloxime photopolymerization initiators represented by general formulas (5) and (6). Among these compounds, O-acyloxime photopolymerization initiators with a molar absorptivity of 10,000 or higher at 365 nm are preferred when using a light-blocking component at a high concentration. Furthermore, the term "photopolymerization initiator" as used in this invention includes the meaning of a sensitizer.

[0050] General formula (5)

[0051] (In equation (5), R9, R 10 Each of the following groups independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, R 11 This refers to alkyl groups having 1 to 15 carbon atoms, aryl groups having 6 to 18 carbon atoms, and arylalkyl groups having 7 to 20 carbon atoms. Here, the alkyl and aryl groups may also be alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, or alkanoyl groups having 1 to 10 carbon atoms, and may be halogenated. The alkylene moiety may also contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group may be any type of straight-chain, branched, or cyclic alkyl group.

[0052] general formula·

[0053] (In equation (6), R) 12and R 13 Each is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl, cycloalkyl-alkyl, or alkyl-cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms. 14 Each is independently a straight-chain or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may also be substituted with -O- groups. Additionally, these R... 12 To R 14 Some hydrogen atoms in the radical can also be replaced by halogen atoms.

[0054] Based on a total of 100 parts by weight of components (A) and (B), 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. When the blending ratio of component (C) is 3 parts by weight or more, the sensitivity is good, and a sufficient photopolymerization rate can be obtained. When the blending ratio of component (C) is 30 parts by weight or less, appropriate sensitivity can be obtained, and the desired pattern linewidth and desired pattern edge can be obtained.

[0055] 4. (D) Component

[0056] In this embodiment, the light-blocking components such as black pigment, mixed pigment, and light-blocking material in component (D) are not particularly limited as long as they are dispersed with an average particle size of 1 to 1000 nm (the average particle size measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter). Well-known light-blocking components can be used.

[0057] Examples of black pigments with component (D) include: perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, etc.

[0058] Examples of mixed pigments containing component (D) include: pigments selected from azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacrine pigments, isoindolinone pigments, isoindolinone pigments, and dioxindoline pigments. Pigments are composed of at least two colors of organic pigments, such as pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and sulfur indigo pigments.

[0059] The above-mentioned component (D) may be used alone or in combination with two or more components, depending on the function of the photosensitive resin composition to which it is intended.

[0060] In addition, examples of organic pigments that can be used in cases where mixed pigments are used as component (D) include, but are not limited to, color index names with the following numbers.

[0061] 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.

[0062] Pigment Orange: 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

[0063] 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.

[0064] Pigment Green 7, 36, 58, etc.

[0065] Pigment Blue in ratios of 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and 80, etc.

[0066] Pigment purple 19, 23, 37, etc.

[0067] The proportion of the light-blocking component in component (D) can be arbitrarily determined according to the desired light-blocking degree, but it is more preferably 20 to 80% by mass relative to the solid content in the photosensitive resin composition, and more preferably 40 to 70% by mass. When using organic pigments such as aniline black, cyanine black, and lactam black, or carbon-based light-blocking components such as carbon black as the light-blocking component in component (D), it is particularly preferred to have a proportion of 40 to 60% by mass relative to the solid content in the photosensitive resin composition. When the light-blocking component is 20% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-blocking properties can be obtained. When the light-blocking component is 80% by mass or less relative to the solid content in the photosensitive resin composition, the content of the photosensitive resin that originally served as a binder will not decrease, and therefore the desired development characteristics and film-forming ability can be obtained.

[0068] The above-mentioned component (D) is usually mixed with other blending components as a light-blocking component dispersion dispersed in a solvent. At this time, a dispersant may be added. There are no particular restrictions on the dispersant, and well-known compounds used to disperse pigments (light-blocking components) (compounds sold under names such as dispersant, wetting agent, dispersion accelerator, etc.) can be used.

[0069] Examples of dispersants include: cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersing aids). Cationic polymeric dispersants are particularly preferred, having cationic functional groups such as imidazole, pyrrole, pyridyl, primary, secondary, or tertiary amine groups as adsorption sites for colorants, an amine value of 1 to 100 mg KOH / g, and a number average molecular weight (Mn) in the range of 1000 to 100000. The amount of this dispersant incorporated is preferably 1 to 35% by mass relative to the opacifying component, more preferably 2 to 25% by mass. Additionally, high-viscosity substances such as resins generally have a stabilizing effect on dispersion, but high-viscosity substances that do not have the ability to promote dispersion are not considered dispersants. However, their use is not limited to stabilizing dispersion.

[0070] 5. (E) Component

[0071] (E) The silica particles of the composition are not particularly limited by manufacturing methods such as gas-phase reaction or liquid-phase reaction, or by shape (spherical or non-spherical).

[0072] The type of silica particles used in component (E) of this invention is not particularly limited. Solid silica particles or hollow silica particles can be used. In addition, "hollow silica particles" refers to silica particles with cavities inside.

[0073] By using the aforementioned silicon oxide particles, the refractive index of the light-shielding film containing these silicon oxide particles can be reduced.

[0074] The average particle size of the aforementioned silica particles is preferably 1 to 100 nm, more preferably 10 to 90 nm. Compared to smaller particle sizes with an average particle size of several nm, it is believed that silica particles within the aforementioned size range are less prone to aggregation. Accordingly, within the aforementioned particle size range, silica particles exhibit excellent dispersion stability and can therefore exist uniformly within the light-shielding film. Consequently, non-uniform reflectivity on the light-shielding film is less likely to occur.

[0075] The average particle size of the aforementioned silica particles can be measured using a particle size analyzer, the FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), which employs dynamic light scattering, and by the cumulative method.

[0076] Furthermore, the content of the aforementioned silica particles is preferably 0.1 to 5 parts by mass relative to the total mass of the photosensitive resin composition, more preferably 0.1 to 2 parts by mass. When the content of silica particles is within the above range, low reflectivity can be achieved, and good patterning performance can be ensured.

[0077] In addition, the aforementioned silicon oxide particles can be silicon oxide particles with a refractive index of 1.10 to 1.47. Besides using general silicon oxide particles with a refractive index of 1.45 to 1.47, the refractive index of the light-shielding film can be further reduced by using hollow silicon oxide particles with a low refractive index compared to the refractive index of the light-shielding film containing only general silicon oxide particles.

[0078] Furthermore, the refractive index of the silicon oxide particles can be obtained from a transparent mixture obtained by processing the silicon oxide particles into powder and mixing them with a standard refractive liquid with a known refractive index. In this case, the refractive index of the standard refractive liquid in the mixture is taken as the refractive index of the silicon oxide particles. Additionally, the refractive index of the silicon oxide particles can be measured using an Abbe refractometer.

[0079] Furthermore, since reflection caused by the refractive index difference between the transparent substrate and the formed light-shielding film can be suppressed, reflection can be suppressed even without additional anti-reflective film on the substrate.

[0080] The silicon oxide particles described above can be either spherical or elliptical. The silicon oxide particles used in this invention are preferably spherical.

[0081] The aforementioned silicon oxide particles preferably have a sphericity of 1.0 to 1.5. As long as the sphericity of the silicon oxide particles is within this range, the particle shape approximates a true sphere. Therefore, the surface smoothness of the film can be maintained by uniformly filling the thin-film light-shielding film, and the aforementioned silicon oxide particles are formed so that they do not protrude from the film surface to the outside. Thus, a light-shielding film with a low refractive index and sufficient strength can be obtained.

[0082] The true sphericity of the aforementioned silica particles can be obtained from the ratio of the longest diameter to the shortest diameter of the particles (the average of any 100 silica particles). Here, the longest and shortest diameters of the silica particles are obtained by photographing the silica particles with a transmission electron microscope and measuring the longest and shortest diameters of the silica particles from the obtained microscope images.

[0083] 6.(F)Ingredients

[0084] The solvent of component (F) includes: a first solvent being propylene glycol monomethyl ether acetate, and a second solvent having a relative permittivity of 10 to 30 at 23°C.

[0085] In solvent (F), the first solvent is propylene glycol monomethyl ether acetate. The content of the first solvent is preferably 10 to 90% by mass relative to the total mass of component (F), more preferably 20 to 80% by mass, and even more preferably 20 to 74% by mass. By using propylene glycol monomethyl ether acetate containing 10 to 90% by mass as the first solvent, the solubility of the binder resin and the dispersibility of the black pigment can be improved.

[0086] Furthermore, the relative permittivity of the second solvent at 23°C is 10 to 30, more preferably 13 to 20, and even more preferably 13 to 18. By using a solvent with a relative permittivity of 10 to 30 at 23°C as the second solvent, the silanol groups on the surface of the silicon oxide particles can be stabilized through solvation, thereby suppressing the aggregation of silicon oxide particles in the inhibitor composition.

[0087] The second solvent mentioned above is preferably a saturated ketone having a chain, branched or cyclic structure with 3 to 12 carbon atoms, or a saturated or unsaturated alcohol having a chain, branched or cyclic structure with 3 to 12 carbon atoms.

[0088] Examples of the second solvent mentioned above include: ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; alcohols such as ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and ethyl lactate; and glycol ethers such as celazor, methyl celazor, ethyl celazor, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-3-methylbutanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. The second solvent is preferably cyclohexanone, ethyl lactate, 3-methoxy-3-methylbutanol, or propylene glycol monoethyl ether, and more preferably cyclohexanone, ethyl lactate, or 3-methoxy-3-methylbutanol.

[0089] The content of the second solvent is preferably 10 to 50% by mass relative to the total mass of solvent (F), more preferably 20 to 50% by mass, and even more preferably 25 to 50% by mass. By keeping the solvent content within the above range, the aggregation of silica particles can be suppressed, and good coatability can be imparted.

[0090] In addition, the relative permittivity of the solvent (F) mentioned above can be measured using a relative permittivity meter “Model 871” (manufactured by Nihon Rufuto Co., Ltd.).

[0091] In addition, the solvent (F) may include a third solvent with a boiling point of 150°C to 350°C at atmospheric pressure, in addition to the first and second solvents described above. The boiling point of the third solvent at atmospheric pressure is preferably 150 to 350°C, and more preferably 160 to 300°C.

[0092] In addition to propylene glycol monomethyl ether acetate as the first solvent and the aforementioned second solvent with a relative permittivity of 10 to 30 at 23°C, a third solvent with a boiling point of 150°C to 350°C at atmospheric pressure may also be used in combination.

[0093] Examples of the third solvent include: acetate esters such as butyl carbitol acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monoethyl ether acetate, and ethyl 3-ethoxypropionate; ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; and terpenes such as α- or β-terpineol. The preferred third solvents are: diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0094] The content of the third solvent is preferably 1 to 30% by mass relative to the total mass of solvent (F), more preferably 1 to 20% by mass. By including the third solvent in the range of 1 to 30% by mass, the agglomeration of silica particles can be suppressed. In addition, by controlling the drying properties of the inhibitor, sudden boiling during vacuum drying and the generation of drying impurities in the coating nozzle can be suppressed.

[0095] Furthermore, the relative permittivity of solvent (F) at 23°C is preferably 8.5 or higher and 15.0 or lower, more preferably 8.8 or higher and 15.0 or lower, and even more preferably 9.3 or higher and 15.0 or lower. By ensuring that the relative permittivity of solvent (F) at 23°C is 8.5 or higher, the silanol groups remaining on the surface of silicon oxide particles can be stabilized by solvent action, thereby suppressing the aggregation of silicon oxide particles. In addition, by ensuring that the relative permittivity at 23°C is 15.0 or lower, the drying performance and good coating properties in the VCD step of drying the solvent under reduced pressure can be ensured. Here, "solvent as a whole" refers to a mixture of the first solvent and the second solvent, or a mixture of the first solvent, the second solvent, and the third solvent.

[0096] In addition, the photosensitive resin composition of the present invention may also be mixed with resins other than component (A) such as epoxy resin, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than silica, leveling agents, defoamers, surfactants, coupling agents and other additives as needed.

[0097] Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyroquinone, tert-butylcatechol, and phenoxythiazolinone. Hindered phenolic compounds, etc. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include: glass fiber, silica, mica, alumina, etc. Examples of defoamers or leveling agents include: polysiloxane, fluorine, and acrylic compounds. Examples of surfactants include: fluorine surfactants, polysiloxane surfactants, etc. Examples of coupling agents include: 3-(glycidoxy)propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, 3-ureopropyltriethoxysilane, etc.

[0098] The photosensitive resin composition of the present invention, after deducting the solvent, preferably comprises, in the following solid components (including monomers that become solid after photocuring): (A) a photosensitive resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-blocking component selected from black pigments, mixed pigments, and light-blocking materials, and (E) silica particles. The amount of solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass relative to the total amount.

[0099] Furthermore, the light-shielding film formed by curing the photosensitive resin composition of the present invention can be obtained, for example, by coating a solution of the photosensitive resin composition onto a substrate, drying the solvent, and irradiating it with light (including ultraviolet light, radiation, etc.) to cure it. By using a photomask or the like to set up light-exposed and non-light-exposed areas, curing only the light-exposed areas, and dissolving the other areas with an alkaline solution, a desired pattern can be obtained.

[0100] In addition, the light-shielding film of the present invention can be used as a color filter or touch panel of a black matrix. For example, it can be manufactured by the following methods: forming a light-shielding film with a thickness of 1.0 to 2.0 μm on a transparent substrate, forming red, blue and green pixels by photolithography after forming the light-shielding film, and spraying red, blue and green inks onto the light-shielding film by inkjet process.

[0101] Furthermore, the light-shielding film formed by curing the photosensitive resin composition of the present invention can also be used as a black column spacer in a liquid crystal display device. For example, multiple portions with different film thicknesses can be made using a single black resist, so that one portion functions as a spacer and the others function as a black matrix.

[0102] Specific examples illustrate the steps in a method for forming a light-shielding film by coating and drying a photosensitive resin composition.

[0103] The method of coating the photosensitive resin composition onto the substrate can employ any well-known method, such as solution dipping, spraying, using a roller coater, land coater, slot coater, or spin coater. After coating to the desired thickness using these methods, the solvent is removed (pre-baking), thereby forming a film. Pre-baking can be performed by heating with an oven, hot plate, or a combination thereof, vacuum drying. The heating temperature and time during pre-baking can be appropriately selected depending on the solvent used, but are preferably performed, for example, at 80 to 120°C for 1 to 10 minutes.

[0104] The radiation used during exposure can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., but the wavelength range of the radiation is preferably 250 to 450 nm. Additionally, suitable developing solutions for this alkaline development include, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developing solutions can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add surfactants as needed. The developing temperature is preferably 20 to 35°C, allowing for precise formation of fine images using commercially available developing machines or ultrasonic washing machines. Furthermore, water washing is usually performed after alkaline development. Developing methods that can be used include: rinsing development, spray development, immersion development, paddle development, etc.

[0105] After development, the film is heat-treated (post-baked) at 180 to 250°C for 20 to 100 minutes. The purpose of this subsequent baking is to improve the adhesion between the patterned cured film (light-shielding film) and the substrate. This baking, similar to pre-baking, can be performed using an oven, heating plate, or similar heating method. The patterned cured film (light-shielding film) of this invention can be formed through various steps in a photolithography process. Then, by thermal polymerization and curing (sometimes referred to together as curing), a light-shielding film with the desired pattern can be obtained.

[0106] The photosensitive resin composition for black resist of the present invention, as described above, is not only suitable for forming fine patterns by exposure, alkaline development and other operations, but also can produce a light-shielding film with excellent light-shielding, adhesion, electrical insulation, heat resistance and chemical resistance even when the pattern is formed by conventional screen printing.

[0107] The photosensitive resin composition for black resist of the present invention is suitable for use as a coating material. It is particularly useful as a color filter ink used in liquid crystal display devices or photographic elements, and as a light-shielding film formed therefrom, for color filters, black matrices for liquid crystal projection, etc. Furthermore, the photosensitive resin composition for black resist of the present invention, in addition to color filter inks for color liquid crystal displays, can also be used as an ink material for distinguishing various colors or for light shielding in various multicolor displays such as organic electroluminescent devices (represented by organic EL elements), color liquid crystal display devices, color fax machines, and image sensors. 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 can be reduced, as well as reflection from light emitted by the element when used in organic EL elements, for example. That is, it is possible to reduce the reflection of external light to improve brightness contrast and improve the efficiency of light extraction from the light-emitting side to improve luminous efficiency.

[0108] [Example]

[0109] Hereinafter, embodiments of the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these embodiments.

[0110] First, examples of the synthesis of alkali-soluble resins containing polymerizable unsaturated groups of component (A) will be described. Unless otherwise stated, the resin evaluation in these examples will be carried out as follows.

[0111] [Solid component concentration]

[0112] 1g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W0(g)] and weighed [W1(g)]. The weight [W2(g)] after heating at 160°C for 2 hours was obtained by the following formula.

[0113] Solid component concentration (wt%) = 100 × (W2 - W0) / (W1 - W0)

[0114] [Acid Value]

[0115] Dissolve the resin solution in two Alkane was obtained by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus “COM-1600” (manufactured by Hiranuma Sangyo Co., Ltd.).

[0116] [Molecular weight]

[0117] The weight-average molecular weight (Mw) was determined using gel osmosis chromatography (GPC) “HLC-8220GPC” (manufactured by TOSOH Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-5000 (1) (manufactured by TOSOH Corporation), temperature: 40℃, speed: 0.6 ml / min) as a conversion value for standard polystyrene (manufactured by TOSOH Corporation, PS-Oligomer Kit).

[0118] [Average Particle Size]

[0119] The average particle size of the silica particles was determined by the cumulative method using a particle size analyzer "FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.

[0120] The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

[0121] BPFE: The reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and 1-chloro-2,3-1-chloromethyloxirane. In compounds of general formula (1), X is fluorene-9,9-diyl and R1 to R4 are hydrogen.

[0122] AA: Acrylic acid

[0123] BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

[0124] THPA: Tetrahydrophthalic anhydride

[0125] TEAB: Tetraethylammonium bromide

[0126] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0127] [Synthesis example]

[0128] In a 500 ml four-necked flask equipped with a reflux condenser, BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were added and stirred at 100-105 °C for 20 hours to allow the reaction to proceed. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask and stirred at 120-125 °C for 6 hours to obtain a alkali-soluble resin (A) containing polymerizable unsaturated groups. The resulting resin solution had a solids content of 56.1% by mass, an acid value (converted from solids content) of 103 mg KOH / g, and a Mw of 3600 obtained by GPC analysis.

[0129] The photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were prepared using the blending amounts (in mass %) listed in Table 1. The blending components used in the table are as follows.

[0130] (Alkali-soluble resins containing polymerizable unsaturated groups)

[0131] (A): The alkali-soluble resin solution obtained in the above synthesis example (solid content concentration 56.1% by mass)

[0132] (Photopolymerizable monomers)

[0133] (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (ARONIX M-405, manufactured by Dong-A Synthetic Co., Ltd., "ARONIX" is a registered trademark of the company).

[0134] (Photopolymerization initiator)

[0135] (C): Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (Irgacure OXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of the company)

[0136] (Carbon black dispersion)

[0137] (D): A PGMEA dispersion of a carbon black concentration of 25.0% by mass, a polymeric dispersant concentration of 5.0% by mass, and a dispersion of a alkali-soluble resin (A) (solid content 5.0% by mass) (solid content 35.0% by mass).

[0138] (E): Silica PGMEA dispersion "YA050C" (manufactured by Admatechs Inc., solid content 40% by mass, average particle size 50nm)

[0139] (solvent)

[0140] (First Solvent)

[0141] (F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0142] (Second solvent)

[0143] (F)-2: Cyclohexanone (ANON)

[0144] (F)-3: Ethyl lactate (EL)

[0145] (F)-4: 3-Methoxy-3-methylbutanol (MMB)

[0146] (F)-5: Propylene glycol monomethyl ether (PGME)

[0147] (Third solvent)

[0148] (F)-6: Diethylene glycol dimethyl ether (MDM)

[0149] (F)-7: Diethylene glycol ethyl methyl ether (EDM)

[0150] (F)-8: Diethylene glycol diethyl ether (EDE)

[0151] (F)-9: Diethylene glycol dibutyl ether (BDB)

[0152]

[0153] [Evaluate]

[0154] A cured film (light-shielding film) made of a photosensitive resin composition for use in evaluation of a cured black resist is prepared as follows.

[0155] (Fabrication of cured film (light-shielding film) for evaluating foreign matter, optical density, and reflectivity)

[0156] To achieve a film thickness of 1.2 μm after heat curing, the film was pre-irradiated with a low-pressure mercury lamp at an illuminance of 1000 mJ / cm² at a wavelength of 254 nm. 2 On a 125mm × 125mm glass substrate "#1737" (manufactured by Corning Corporation) (hereinafter referred to as "glass substrate") that has been washed with ultraviolet light, the photosensitive resin composition shown in Table 1 is applied by spin coating, and the substrate is pre-baked at 90°C for 1 minute using a hot plate to produce a dried light-shielding film. Then, the entire surface of the dried light-shielding film is subjected to an ultraviolet illuminance of 30mW / cm². 2 Irradiation with an ultra-high pressure mercury lamp at 50 mJ / cm 2 The ultraviolet light is used to perform a photocuring reaction on the light-shielding film.

[0157] Next, it was passed through a 25°C, 0.04% potassium hydroxide solution at a concentration of 1 kgf / cm³. 2 After being exposed to the above-mentioned cured film (light-shielding film) and subjected to a 1-minute development process at a rinsing pressure of 5 kgf / cm², the film was then subjected to further processing. 2 The developed light-shielding film was sprayed and washed with water, and then formally cured (post-baked) at 230°C for 30 minutes using a hot air dryer to obtain the cured films (light-shielding films) of Examples 1 to 14 and Comparative Examples 1 to 8.

[0158] The following evaluation items were performed on the cured films (light-shielding films) made from the photosensitive resin compositions of the curable black resists of Examples 1 to 14 and Comparative Examples 1 to 8 obtained above.

[0159] [Foreign Object Assessment]

[0160] (Assessment Methodology)

[0161] Use a microscope to observe the cured film (light-shielding film) after formal curing (post-baking) to confirm the absence of foreign matter originating from the condensate. Additionally, a value of △ or higher is considered acceptable.

[0162] (Evaluation criteria for foreign object assessment)

[0163] ○: No foreign matter originating from condensates was identified in the cured film (light-shielding film).

[0164] △: Foreign matter originating from condensates was confirmed in a portion of the cured film (light-shielding film).

[0165] ×: Foreign matter originating from condensates was confirmed to be present across the entire surface of the cured film (light-shielding film).

[0166] [Optical Concentration Assessment]

[0167] (Assessment Methodology)

[0168] The optical density (OD) of the cured film (light-shielding film) was evaluated using a Macbeth penetration density meter. Additionally, the thickness of the cured film (light-shielding film) formed on the substrate was measured, and the OD value was divided by the film thickness as OD / μm.

[0169] Optical density (OD) is calculated using the following formula (1).

[0170] Optical concentration (OD) = -log10T (1)

[0171] (T represents penetration rate)

[0172] [Reflectivity Assessment]

[0173] (Assessment Methodology)

[0174] For a substrate with a cured film (light-shielding film) manufactured using the same method as the cured film (light-shielding film) used for optical density (OD) evaluation, the reflectance of the substrate (glass substrate) side was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi Hightech Science Co., Ltd.) at an incident angle of 2°.

[0175] [Evaluation of Uneven Coating]

[0176] (Assessment Methodology)

[0177] (Preparation of the curing film (light-shielding film) for evaluating uneven coating)

[0178] To achieve a film thickness of 1.2 μm after heat curing, the film was pre-irradiated with a low-pressure mercury lamp at a wavelength of 254 nm and an illuminance of 1000 mJ / cm². 2 On a 125mm × 125mm glass substrate "#1737" (manufactured by Corning Corporation) (hereinafter referred to as "glass substrate") with a washed surface exposed to ultraviolet light, the photosensitive resin composition shown in Table 1 was coated using a spin coating method. The substrate was then dried under vacuum at 200 Pa for 1 minute using a VCD, and pre-baked at 90°C for 1 minute using a heated plate to produce a dried light-shielding film. Next, the obtained dried light-shielding film was formally cured (post-baked) at 230°C for 30 minutes to obtain the cured films (light-shielding films) of Examples 1 to 14 and Comparative Examples 1 to 8.

[0179] (Assessment Methodology)

[0180] Visually inspect the cured film (light-shielding film) after formal curing (post-baking) to confirm the uniformity of the coating. Additionally, a value of △ or higher is considered acceptable.

[0181] (Evaluation criteria for coating unevenness assessment)

[0182] ○: No unevenness was detected in the cured film (light-shielding film).

[0183] △: Unevenness was detected in a portion of the cured film (light-shielding film).

[0184] ×: The cured film (light-shielding film) was not applied evenly; unevenness was observed across the entire surface.

[0185] The above assessment results are shown in Table 2.

[0186]

[0187] As shown in Examples 1 to 14, it is evident that by including a second solvent with a relative permittivity of 10 to 30 at 23°C and setting the overall relative permittivity of the solvent at 23°C to 8.5 or higher, a light-shielding film with high light-shielding properties, low reflectivity, and suppressed agglomerate formation can be obtained. It is speculated that by setting the relative permittivity of the second solvent to 10 to 30 and setting the overall relative permittivity of the solvent at 23°C to 8.5 or higher, the silanol groups remaining on the surface of the silicon oxide particles can be stabilized through solvent interaction.

[0188] In particular, in Examples 1 to 3, 7 to 11, 13, and 14, where the content of the second solvent at 23°C and having a relative permittivity of 13 or higher was 20 to 50% by mass relative to all solvents, the formation of agglomerates observed in Comparative Examples 4 to 8 was significantly suppressed, and no decrease in optical concentration was observed. This suggests that the aforementioned second solvent with a high relative permittivity can more effectively solvate the silanol groups on the surface of silicon oxide particles.

[0189] In Examples 9 to 14, which contain a third solvent, in addition to the suppression of aggregates of silica particles as a result of the effect of the second solvent, the drying properties are also improved by the effect of the third solvent with a high boiling point, thereby suppressing uneven coating.

[0190] [Industry availability]

[0191] According to the photosensitive resin composition of the present invention, a photosensitive resin composition for a black matrix with both high light-blocking properties and low reflectivity can be provided, as well as a light-blocking film using the photosensitive resin composition, a color filter, and a touch panel. Furthermore, various display devices with excellent readability can be provided through the color filter and the touch panel.

Claims

1. A photosensitive resin composition for use as a black resist, comprising the following components as essential components: (A) Photosensitive resins containing unsaturated groups, (B) Photopolymerizable monomers with at least two unsaturated bonds, (C) Photopolymerization initiator, (D) At least one opaque component selected from black pigments and mixed pigments; (E) Silica particles, and (F) Solvent; The aforementioned solvent (F) comprises a first solvent being propylene glycol monomethyl ether acetate and a second solvent having a relative permittivity of 10 to 30 at 23°C; The aforementioned second solvent is ethyl lactate or 3-methoxy-3-methylbutanol; The content of the second solvent mentioned above is 25% to 50% by mass relative to the total mass of the solvent (F) mentioned above. The aforementioned solvent (F) has a relative permittivity of 8.5 or higher at 23°C.

2. A photosensitive resin composition for use as a black resist, comprising the following components as essential components: (A) Photosensitive resins containing unsaturated groups, (B) Photopolymerizable monomers with at least two unsaturated bonds, (C) Photopolymerization initiator, (D) At least one opaque component selected from black pigments and mixed pigments; (E) Silica particles, and (F) Solvent; The aforementioned solvent (F) comprises a first solvent being propylene glycol monomethyl ether acetate, a second solvent having a relative permittivity of 10 to 30 at 23°C, and a third solvent having a boiling point of 150°C to 350°C at atmospheric pressure. The aforementioned second solvent is ethyl lactate or 3-methoxy-3-methylbutanol; The content of the second solvent mentioned above is 20% to 50% by mass relative to the total mass of the solvent (F) mentioned above. The aforementioned third solvent is diethylene glycol ethyl methyl ether or diethylene glycol dibutyl ether; The aforementioned solvent (F) has a relative permittivity of 8.5 or higher at 23°C.

3. The photosensitive resin composition for black resist according to claim 1 or 2, wherein, The aforementioned (A) photosensitive resin containing unsaturated groups is a photosensitive resin containing unsaturated groups obtained by further reacting a bisphenol-derived epoxide having two glycidyl ether groups, represented by general formula (1), with (meth)acrylic acid to a polycarboxylic acid or its anhydride. In general formula (1), R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl atom with 1 to 5 carbon atoms or a halogen atom, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or single bond represented by general formula (2), and l is an integer from 0 to 10; 。 4. A light-shielding film, wherein the black resist of any one of claims 1 to 3 is cured with a photosensitive resin composition.

5. A color filter having the light-shielding film of claim 4 as a black matrix.

6. A touch panel having the light-shielding film of claim 4 as a black matrix.

7. A display device having a color filter as claimed in claim 5 or a touch panel as claimed in claim 6.

Images