Photosensitive resin composition for black resist, light-shielding film obtained by curing the same, and color filter

Abstract

To provide a photosensitive resin composition for black resist which has light-shielding properties and low reflectance, a light-shielding film obtained by curing the same, and a color filter.SOLUTION: A photosensitive resin composition for black resist contains: (A) an unsaturated group-containing photosensitive resin; (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material; and (E) silica particles. The silica particles, the component (E), are hollow particles.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition for black resist, and a light-shielding film and a color filter obtained by curing the same. [Background technology]

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

[0003] In display devices and the like, in order to suppress light leakage and the like and improve the visibility of the screen of the display device and the like, the concentration of the black pigment in the light-shielding film may be increased to increase the light-shielding property of the light-shielding film (reduce the light transmittance of the light-shielding film). Since the refractive index of the black pigment is higher than that of the transparent substrate and the curable resin, increasing the concentration of the black pigment in the light-shielding film increases the reflectance when viewed from the side opposite to the side on which the light-shielding film of the transparent substrate is formed. This increases the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate, causing problems such as reflection on the light-shielding film and the black matrix boundary being noticeable due to the difference in reflectance with the colored part of the color filter.

[0004] For this reason, there is a demand for a photosensitive resin composition for black resist having both high light-shielding properties and low reflectance, and a light-shielding film and a color filter obtained by curing the same.

[0005] For example, Patent Document 1 discloses a black photosensitive resin composition that is characterized by containing hydrophobic silica fine particles and a specific dispersant (urethane-based dispersant). It is said that the use of hydrophobic silica fine particles and the specific dispersant makes it possible to form a black matrix that achieves both high light-shielding properties and low reflectance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2015-161815 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the inventors of the present invention have found that a light-shielding film having both high light-shielding properties and low reflectance could not be obtained using the black photosensitive resin composition described in Patent Document 1. In addition, in light-shielding films for sensors such as various display devices and solid-state imaging devices, depending on the design of the device configuration, not only is it necessary to reduce the reflectance of the transparent substrate side of the light-shielding film applied to a transparent substrate such as glass, but there are also cases where it is required to reduce the reflectance of the surface opposite to the surface in contact with the transparent substrate (hereinafter referred to as the "coated surface").

[0008] The present invention has been made in view of the above-mentioned points, and an object of the present invention is to provide a photosensitive resin composition for black resist having high light-shielding properties and low reflectance, and a light-shielding film and a color filter obtained by curing the same. [Means for solving the problem]

[0009] The photosensitive resin composition for black resist according to the present invention comprises (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material, and (E) silica particles, and the silica particles as component (E) are hollow particles.

[0010] The light-shielding film according to the present invention is composed of the above-mentioned photosensitive resin composition for black resist.

[0011] The color filter according to the present invention has the above-mentioned light-shielding film as a black matrix. Effect of the Invention

[0012] According to the present invention, it is possible to provide a photosensitive resin composition for black resist having high light-shielding property and low reflectance, and a light-shielding film and a color filter using the same. Furthermore, when the light-shielding film of the present invention is formed on a transparent substrate, it can contribute to realizing low reflectance not only on the transparent substrate side but also on the coated surface side of the light-shielding film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. The photosensitive resin composition for black resist of the present invention (hereinafter, abbreviated as photosensitive resin composition) contains components (A) to (E). Components (A) to (E) will be described below.

[0014] (Component (A)) The unsaturated group-containing photosensitive resin, which is the component (A), preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably has both a polymerizable unsaturated group and a carboxyl group. The above resin can be widely used without any particular limitation.

[0015] An example of the unsaturated group-containing photosensitive resin is an epoxy (meth)acrylate acid adduct obtained by reacting an epoxy compound having two glycidyl ether groups derived from a bisphenol (hereinafter also referred to as a "bisphenol-type epoxy compound represented by general formula (1)") with (meth)acrylic acid, and reacting the resulting compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. An epoxy compound derived from a bisphenol means an epoxy compound obtained by reacting a bisphenol with an epihalohydrin, or an equivalent thereof. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and means either or both of them.

[0016] The unsaturated group-containing photosensitive resin, component (A), is preferably a bisphenol-type epoxy compound represented by general formula (1).

[0017] [ka] (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-, a fluorene-9,9-diyl group represented by formula (2), or a single bond, and l is an integer of 0 to 10.

[0018] [ka]

[0019] The bisphenol epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore contains an epoxy compound having two or more bisphenol skeletons.

[0020] Examples of bisphenols that can be 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-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, and bis(4-hydroxyphenyl)hexafluoropropane. 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)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 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 these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0021] Examples of (a) dicarboxylic acid or tricarboxylic acid monoanhydrides that react with the hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Furthermore, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced are also included. Examples of the monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc. Furthermore, monoanhydrides of dicarboxylic or tricarboxylic acids into which an arbitrary substituent has been introduced, etc. Furthermore, examples of the monoanhydrides of aromatic dicarboxylic or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, etc. Furthermore, monoanhydrides of dicarboxylic or tricarboxylic acids into which an arbitrary substituent has been introduced, etc.

[0022] Examples of the (a) dicarboxylic acid or tricarboxylic acid monoanhydride that reacts with the hydroxy group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of the acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Furthermore, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced are also included. Examples of the monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc. Furthermore, monoanhydrides of dicarboxylic or tricarboxylic acids into which an arbitrary substituent has been introduced, etc. Furthermore, examples of the monoanhydrides of aromatic dicarboxylic or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, etc. Furthermore, monoanhydrides of dicarboxylic or tricarboxylic acids into which an arbitrary substituent has been introduced, etc.

[0023] The molar ratio (a) / (b) of (a) dicarboxylic or tricarboxylic acid anhydride and (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) deviates from the above range, it is not preferable because the optimal molecular weight for making a photosensitive resin composition having good photopatterning properties cannot be obtained. Note that the smaller the molar ratio (a) / (b), the larger the molecular weight and the lower the alkali solubility.

[0024] The reaction between the epoxy compound and (meth)acrylic acid, and the reaction between the epoxy (meth)acrylate obtained by this reaction and the polybasic acid or its acid anhydride are not particularly limited, and known methods can be adopted. The unsaturated group-containing photosensitive resin synthesized by the above reaction preferably has a weight average molecular weight (Mw) of 2000 to 10000 and an acid value of 30 to 200 mg / KOH.

[0025] Another example of a resin preferable as the unsaturated group-containing photosensitive resin of component (A) includes a copolymer of (meth)acrylic acid, (meth)acrylic acid esters, etc., and a resin having a (meth)acryloyl group and a carboxy group. Examples of the resin include a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a copolymer obtained by copolymerizing (meth)acrylic acid esters including glycidyl (meth)acrylate in a solvent with the copolymer, and finally reacting with an anhydride of a dicarboxylic acid or tricarboxylic acid. The above copolymer is shown in JP 2014-111722 A, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and has a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mg KOH / g. Also, JP 2018-141968 A shows a polymerizable unsaturated group-containing alkali-soluble resin which is a polymer having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mg / KOH, which includes 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.

[0026] Regarding the unsaturated group-containing photosensitive resin of the component (A), one type may be used alone, or two or more types may be used in combination.

[0027] ((B) component) Examples of the photopolymerizable monomer having at least two ethylenically unsaturated bonds in the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. The monomers include (meth)acrylic acid esters such as tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, and caprolactone modified dipentaerythritol hexa(meth)acrylate, and dendritic polymers having a (meth)acrylic group as a compound having an ethylenic double bond. Only one of these monomers may be used alone, or two or more may be used in combination. In addition, the photopolymerizable monomer having at least two ethylenic unsaturated bonds can play a role of crosslinking the molecules of the contained alkali-soluble resin, and in order to exert this function, it is preferable to use one having three or more photopolymerizable groups. Furthermore, the acrylic equivalent, calculated by dividing the molecular weight of the monomer by the number of (meth)acrylic groups in one molecule, is preferably from 50 to 300, and more preferably from 80 to 200. The component (B) does not have a free carboxy group.

[0028] An example of a dendritic polymer having a (meth)acryloyl group as a compound having an ethylenic double bond that can be contained in the composition as component (B) is a dendritic polymer obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, it includes a dendritic polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (3) with a polyvalent mercapto compound represented by general formula (4).

[0029] [ka] (In formula (3), R 5 is a hydrogen atom or a methyl group, and R 6 is R 7 (OH) k The remaining portion is obtained by donating n hydroxy groups out of k hydroxy groups to the ester bond in the formula. 7 (OH) k is a polyhydric alcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking a plurality of molecules of the polyhydric alcohol via ether bonds by dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. k and n independently represent integers of 2 to 20, provided that k≧n.

[0030] [ka] (In formula (4), R 8 is a single bond or a divalent to hexavalent C1 to C6 hydrocarbon group, and m is R 8 is a single bond, R 8 When is a divalent to hexavalent group, it is an integer of 2 to 6.

[0031] Examples of the polyfunctional (meth)acrylate represented by the general formula (3) include (meth)acrylic acid esters such as 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, and caprolactone modified pentaerythritol tri(meth)acrylate. These compounds may be used alone or in combination of two or more.

[0032] Examples of polyvalent mercapto compounds represented by general formula (4) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. These compounds may be used alone or in combination of two or more.

[0033] The blending ratio of the (A) component to the (B) component is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20, in terms of the weight ratio (A) / (B). When the blending ratio of the (A) component is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to become low in the unexposed areas, so that the decrease in solubility in an alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges and lack of sharpness are less likely to occur. In addition, when the blending ratio of the (A) component is 90 / 10 or less, the ratio of photoreactive functional groups in the resin is sufficient, so that the desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in an alkaline developer in the exposed areas is less likely to increase, so that the formed pattern is less likely to be narrower than the target line width, and pattern loss can be suppressed.

[0034] ((C) component) Examples of the (C) photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoin ethers; biimidazole compounds such as 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, and 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl halomethylthiazole compounds such as 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-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, halomethyl-S-triazine compounds such as 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine;O-acyloxime compounds such as 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-acetyloxime; benzyl dimethyl ketal, thioxanthone, Examples of the photopolymerization initiator include sulfur compounds such as 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; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination of two or more kinds.

[0035] In particular, when preparing a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxime compounds (including ketoximes). Examples of compounds that can be preferably used include O-acyloxime photopolymerization initiators represented by general formulas (5) and (6). Among these compounds, when using a colorant at a high pigment concentration or forming a light-shielding film pattern, it is preferable to use an O-acyloxime photopolymerization initiator having a molar absorption coefficient of 10,000 or more at 365 nm. In the present invention, the term "photopolymerization initiator" is used to include sensitizers.

[0036] [ka] (In formula (5), R9 , R 10 each independently represents a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group; R 11 represents a C1-C15 alkyl group, a C6-C18 aryl group, or a C7-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 portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups.

[0037] [ka] (In formula (6), R 12 and R 13 R 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 phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 14 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and -CH 2 A part of the - groups may be replaced by -O- groups. 12 ~R 14 A part of the hydrogen atoms in the group may be substituted with halogen atoms.

[0038] The amount of the photopolymerization initiator (C) used 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 the components (A) and (B). When the blending ratio of the component (C) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization speed can be obtained. When the blending ratio of the component (C) is 30 parts by weight or less, the sensitivity is appropriate, so that the desired pattern line width and desired pattern edge can be obtained.

[0039] ((D) component) The light-shielding components such as black pigments, mixed-color organic pigments and light-shielding materials of component (D) that can be used in the present invention are any known light-shielding components that can be used without particular limitation, so long as they are dispersed with an average particle size of 1 to 1000 nm (average particle size measured with a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter).

[0040] Examples of the black pigment of component (D) include perylene black, cyanine black, aniline black, lactam black, carbon black, and titanium black.

[0041] Examples of the mixed-color organic pigment of component (D) include a pigment in which at least two colors are mixed and selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

[0042] The component (D) may be used alone or in combination of two or more types depending on the intended function of the photosensitive resin composition.

[0043] In addition, examples of organic pigments that can be used when a mixed color organic pigment is used as component (D) include, but are not limited to, those having the following Color Index names: 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.

[0044] The blending ratio of the light-shielding component of the component (D) can be arbitrarily determined according to the desired light-shielding degree, but is preferably 20 to 80 mass % relative to the solid components in the photosensitive resin composition, and more preferably 40 to 70 mass %. When an organic pigment such as aniline black, cyanine black, lactam black, or a carbon-based light-shielding component such as carbon black is used as the light-shielding component of the component (D), it is particularly preferable that the blending ratio is 40 to 60 mass % relative to the solid components in the photosensitive resin composition. When the light-shielding component is 20 mass % or more relative to the solid components in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light-shielding component is 80 mass % or less relative to the solid components in the photosensitive resin composition, the content of the photosensitive resin that is the original binder is not reduced, and the desired development characteristics and film-forming ability can be obtained.

[0045] The above-mentioned (D) component is usually mixed with other blending components as a light-shielding component dispersion dispersed in a solvent, and in this case, a dispersant can be added. The dispersant can be any known compound (compounds commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) used for dispersing pigments (light-shielding components) without any particular restrictions.

[0046] Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). In particular, the dispersant is preferably a cationic polymer dispersant having 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 to the colorant, an amine value of 1 to 100 mgKOH / g, and a number average molecular weight (Mn) in the range of 1000 to 100000. The blending amount of this dispersant is preferably 1 to 35 mass % relative to the light-shielding component, and more preferably 2 to 25 mass %. Note that, although high-viscosity substances such as resins generally have the effect of stabilizing dispersion, those that do not have the ability to promote dispersion are not treated as dispersants. However, there is no restriction on using them for the purpose of stabilizing dispersion.

[0047] ((E) component) The silica particles, which are the component (E), are not particularly limited with respect to the production method, such as a gas phase reaction or a liquid phase reaction, and the shape, such as spherical or non-spherical.

[0048] The silica particles as component (E) used in the present invention are preferably hollow silica particles. Note that "hollow silica particles" refer to silica particles having a cavity inside the particle.

[0049] As the silica particles described above, the silica particles that contain gas in the particles have high dispersibility, so that the pattern linearity of the cured film (light-shielding film) that is obtained by curing the photosensitive resin composition of the present invention is good.In addition, by using the silica particles that contain gas in the particles, the refractive index of the light-shielding film that contains the silica particles can be reduced.

[0050] The average particle size of the silica particles is preferably 40 to 100 nm, more preferably 50 to 80 nm. When the average particle size is within the above range, the mechanical strength of the silica particles themselves is high, so that the particles are unlikely to break even if they are hollow. In addition, compared with a small particle size of several nm, it is considered that the silica particles are unlikely to aggregate with each other when the size is within the above range. As a result, the silica particles have excellent dispersion stability within the above particle size range, so that they can exist uniformly in the light-shielding film. Therefore, the reflectance on the light-shielding film is unlikely to vary.

[0051] Furthermore, within the above range, the ratio of hollows inside the silica particles (hereinafter referred to as porosity) can also be adjusted. Since the refractive index of the silica particles varies depending on the particle diameter, it is easy to adjust the refractive index of the light-shielding film regardless of the material of the transparent substrate. Note that "porosity" refers to the ratio of hollows within the particles.

[0052] The average particle size of the silica particles can be determined by randomly selecting 100 particles, measuring the major axis length and minor axis length of the particles, and calculating the arithmetic mean of these. The average particle size of the silica particles can be measured by the cumulant method using a dynamic light scattering particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

[0053] The refractive index of the silica particles is preferably 1.10 to 1.41, and more preferably 1.10 to 1.35. By using the silica particles having a lower refractive index compared to the refractive index (1.45 to 1.47) of normal silica particles, the refractive index of the light-shielding film can be made lower than the refractive index of a light-shielding film containing only normal silica particles.

[0054] The refractive index of the silica particles can be determined from a transparent mixture obtained by mixing the silica particles powdered with a standard refractive index liquid having a known refractive index. In this case, the refractive index of the standard refractive index liquid of the mixture is taken as the refractive index of the silica particles. The refractive index of the silica particles can be measured using an Abbe refractometer.

[0055] The silica particles have a higher porosity, so that the refractive index can be lowered. Therefore, the porosity of the silica particles is preferably 20% by volume or more, more preferably 20 to 95% by volume, more preferably 25 to 90% by volume, even more preferably 30 to 90% by volume, and particularly preferably 35 to 90% by volume. When the porosity is within the above range, a light-shielding film having a desired refractive index can be easily obtained. In addition, reflection caused by the difference in refractive index between the transparent substrate and the light-shielding film formed can be suppressed, so that reflection can be suppressed without providing an anti-reflection film or the like separately on the substrate.

[0056] In addition, by making the porosity of the silica particles within the above range, the weight of the silica particles can be lighter than that of normal silica particles.Therefore, unlike normal silica particles, the silica particles are considered to be less likely to settle toward the transparent substrate side even in the photosensitive resin composition and in the state of being applied on the transparent substrate.As a result, the silica particles are uniformly dispersed in the light-shielding film, so that not only the reflectance when viewed from the transparent substrate side, but also the reflectance when viewed from the cured film side (light-shielding film surface side) can be reduced.

[0057] The porosity of the silica particles can be determined by using a transmission electron microscope. The hollow parts of the silica particles have a low density, and the contrast of the hollow parts is low in a transmission electron microscope photograph, so that the outer shell part and the hollow parts of the silica particles can be confirmed. From the microscope photograph, the longest and shortest diameters of the silica particles are first measured, and the average value is used as the particle diameter of the particle, and the volume (V 1Next, the longest and shortest diameters of the cavity of the particle are measured, and the average value is used as the cavity diameter. The volume (V 2 ) is calculated. The porosity is calculated by the volume (V 1 ) to volume (V 2 ) can be expressed as a percentage.

[0058] As described above, the shape of the silica particles is not particularly limited as long as it has a desired porosity. It may be a true sphere or an ellipse. The shape of the silica particles used in the present invention is preferably a true sphere.

[0059] The silica particles preferably have a sphericity of 1.05 to 1.5. If the sphericity of the silica particles is within this range, the particle shape will be close to a perfect sphere. This allows the silica particles to be uniformly filled in a thin light-shielding film, and the light-shielding film can be formed in which the silica particles are not exposed to the outside from the film surface while maintaining the film surface smoothness. This allows a light-shielding film to be obtained that has a low refractive index and sufficient strength.

[0060] The sphericity of the silica particles can be determined from the ratio of the longest diameter to the shortest diameter (average value of 100 arbitrary silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values ​​determined by photographing the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the silica particles from the obtained micrograph.

[0061] The dispersion used in the photosensitive resin composition of the present invention can be prepared by mixing and dispersing the above components (A) to (E) by an appropriate method.

[0062] (solvent) In addition to the components (A) to (E), the photosensitive resin composition of the present invention preferably contains a solvent as component (F). 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, and propylene glycol monoethyl ether. Examples of the ethyl acetate include glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetate esters such as 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, and propylene glycol monoethyl ether acetate. By dissolving and mixing these alone or in combination of two or more kinds, a uniform solution-like composition can be obtained.

[0063] Furthermore, the photosensitive resin composition of the present invention may contain additives such as a resin other than the component (A), such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler other than hollow silica, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent, as necessary.

[0064] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include glass fiber, silica, mica, alumina, and the like. Examples of defoamers and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0065] The photosensitive resin composition of the present invention preferably contains 80% by mass or more, more preferably 90% by mass or more, of the unsaturated group-containing photosensitive resin (A), the photopolymerizable monomer having at least two ethylenically unsaturated bonds (B), the photopolymerization initiator (C), the light-shielding component (D), and the hollow silica particles (E) in a total amount of 80% by mass or more, more preferably 90% by mass or more, in the solid content (including the monomer that becomes a solid content after curing) excluding the solvent (F). The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass of the total amount.

[0066] A light-shielding film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent, and curing by irradiating with light (including ultraviolet light, radiation, etc.). A desired pattern can be obtained by providing areas exposed to light and areas not exposed to light using a photomask or the like, curing only the areas exposed to light, and dissolving the other areas with an alkaline solution.

[0067] Furthermore, a color filter having the light-shielding film of the present invention as a black matrix can be produced, for example, by forming a light-shielding film having a thickness of 1.0 to 2.0 μm on a transparent substrate, and forming red, blue and green pixels by photolithography after forming the light-shielding film, or by injecting red, blue and green inks into the light-shielding film by an inkjet process.

[0068] The light-shielding film obtained by curing the photosensitive resin composition of the present invention can also be used as a black column spacer for a liquid crystal display device. For example, a single black resist can be used to prepare a plurality of portions with different film thicknesses, one of which can function as a spacer and the other as a black matrix.

[0069] Each step of the method for forming a light-shielding film by coating and drying a photosensitive resin composition will be specifically illustrated.

[0070] The photosensitive resin composition can be applied to a substrate by any of the known methods, such as a solution immersion method, a spray method, a method using a roller coater, a land coater, a slit coater, or a spinner. After applying the composition to a desired thickness by these methods, the solvent is removed (prebaked) to form a coating. Prebaking is performed by heating in an oven or a hot plate, vacuum drying, or a combination of these. The heating temperature and heating time in prebaking can be appropriately selected depending on the solvent used, but it is preferable to perform the prebaking at 80 to 120°C for 1 to 10 minutes, for example.

[0071] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, and the wavelength range of the radiation is preferably 250 to 450 nm. Examples of developers suitable for this alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. These developers can be appropriately selected according to the characteristics of the resin layer, and it is also effective to add a surfactant as necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine or ultrasonic cleaner. After alkaline development, the film is usually washed with water. Examples of development methods that can be used include shower development, spray development, dip (immersion) development, and puddle (liquid puddle) development.

[0072] After the development, a 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 increasing the adhesion between the patterned cured film (light-shielding film) and the substrate. This is performed by heating with an oven, a hot plate, or the like, as in the pre-baking. The patterned cured film (light-shielding film) of the present invention is formed through each process by the photolithography method. Then, polymerization or curing (both may be collectively 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.

[0073] As described above, the photosensitive resin composition for black resist of the present invention is not only suitable for forming a fine pattern by procedures such as exposure to light and alkali development, but also capable of forming a pattern by conventional screen printing to obtain a light-shielding film having similar excellent light-shielding properties, adhesion, electrical insulation properties, heat resistance, and chemical resistance.

[0074] The photosensitive resin composition for black resist of the present invention can be suitably used as a coating material. In particular, the ink for color filters used in liquid crystal display devices or imaging devices, and the light-shielding film formed therefrom are useful as color filters, black matrices for liquid crystal projection, and the like. The photosensitive resin composition for black resist of the present invention can be used as an ink material for color separation or light-shielding in various multicolor display devices such as organic electroluminescent devices represented by organic EL devices, color liquid crystal display devices, color facsimiles, and image sensors, in addition to the color filter ink for color liquid crystal displays. According to the color filter of the present invention, it is possible to reduce the reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, and, for example, the reflection of light emitted from the element when used in an organic EL element. In other words, it is possible to realize an improvement in bright contrast by reducing the reflection of external light, and an improvement in light emission efficiency by improving the light extraction efficiency from the light-emitting side. EXAMPLES

[0075] Hereinafter, the embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

[0076] First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin, which is the component (A), will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0077] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was poured into a glass filter (weight: W 0 (g)] and weighed [W 1 (g)], and the weight after heating at 160°C for 2 hours [W 2 (g)] was calculated using the following formula: Solid content concentration (wt%)=100×(W 2 -W 0 ) / (W 1 -W 0 )

[0078] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0079] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0080] [Average particle size] The average particle size of the silica 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.).

[0081] [Refractive index] The refractive index of the silica particles was determined using an Abbe refractometer.

[0082] [Porosity] The porosity of the silica particles was determined using a transmission electron microscope.

[0083] The abbreviations used in the Synthesis Examples and Comparative Synthesis Examples are as follows. BPFE: 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyl Reaction product with oxirane. In the compound of formula (1), X is fluoro. 9,9-ren-diyl, R 1 , R 2 is a compound of hydrogen. AA: Acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0084] [Synthesis example] BPFE (114.4g, 0.23mol), AA (33.2g, 0.46mol), PGMEA (157g) and TEAB (0.48g) were charged into a 500ml four-neck flask equipped with a reflux condenser, and the mixture was stirred at 100-105°C for 20 hours to react. Next, BPDA (35.3g, 0.12mol) and THPA (18.3g, 0.12mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A). The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content equivalent) was 103mgKOH / g, and the Mw by GPC analysis was 3600.

[0085] Photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared in the amounts (values ​​are mass %) shown in Table 1. The components used in the table are as follows.

[0086] (Polymerizable unsaturated group-containing alkali-soluble resin) (A): Alkali-soluble resin solution obtained in the above synthesis example (solid content concentration: 56.1% by mass)

[0087] (Photopolymerizable monomer) (B): Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate A mixture of acrylate and methacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd.) "Aronix" is a registered trademark of the company.)

[0088] (Photopolymerization initiator) (C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazone] Irgac-3-yl]-, 1-(0-acetyloxime) ure OXE-02, manufactured by BASF Japan, "Irgacure" is a registered trademark of the company) (C)-2: ADEKA Arcles NCI-831, manufactured by ADEKA Corporation, "ADEKA Arcles "Cruise" is a registered trademark of the company.

[0089] (Carbon black dispersion) (D): Carbon black concentration 25.0% by mass, polymer dispersant concentration 10.0% by mass PGMEA dispersion (solid content 34.8% by mass)

[0090] (Silica dispersion) (E)-1: Hollow silica isopropanol dispersion sol (JGC Catalysts and Chemicals, solid content 20% by weight, average particle size approx. 50 nm, Porosity 30% by volume, refractive index 1.30) (E)-2: Hollow silica isopropanol dispersion sol (JGC Catalysts and Chemicals, solid content 20% by weight, average particle size approx. 60 nm, Porosity 37% by volume, refractive index 1.25) (E)-3: Hollow silica isopropanol dispersion sol (JGC Catalysts and Chemicals, solid content 20% by weight, average particle size approx. 75 nm, Porosity 46% by volume, refractive index 1.21) (E)-4: Hollow silica PGMEA dispersion sol (JGC Catalysts and Chemicals, solid content 20% by weight, average particle size approx. 75 nm, Porosity 46% by volume, refractive index 1.25) (E)-5: Solid silica isopropanol dispersion sol (Nissan Chemical Co., Ltd., solid content 30% by weight, average particle size approx. 80 nm, void 0% by volume, refractive index 1.46)

[0091] (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (F)-2: Cyclohexanone (ANON)

[0092] [Example] Photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared in the amounts (values ​​are parts by mass) shown in Table 1. The ingredients used in the table are as follows. Note that (F)-1 and (F)-2 are amounts that do not include the solvents in (A) and (D)-4 and the solvent in (E).

[0093] [Table 1]

[0094] [evaluation] The photosensitive resin compositions for black resist of Examples 1 to 5 and Comparative Examples 1 and 2 were used to carry out the following evaluations.

[0095] (Creation of hardened film (light-shielding film) for evaluating development characteristics) The photosensitive resin composition shown in Table 1 was previously exposed to a low-pressure mercury lamp with an illumination intensity of 1000 mJ / cm at a wavelength of 254 nm. 2 The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 nm so that the film thickness after heat curing would be 1.2 μm, and the coating was prebaked at 90°C for 1 minute using a hot plate to produce a hardened film (light-shielding film). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with a line / space of 10 μm / 50 μm was placed on the dried light-shielding film, and the i-line illuminance was 30 mW / cm. 2 50mJ / cm with ultra-high pressure mercury lamp 2 The exposed portion was exposed to ultraviolet light to cause a photocuring reaction.

[0096] Next, the exposed cured film (light-shielding film) was immersed in a 0.04% potassium hydroxide solution at 25° C. at 1 kgf / cm 2 After developing for +10 and +20 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was 5 kgf / cm 2The unexposed portions of the cured film (light-shielding film) were removed to form a cured film pattern on the glass substrate, and the cured film was post-baked at 120°C for 60 minutes using a hot air dryer to obtain the cured films (light-shielding films) of Examples 1 to 5 and Comparative Examples 1 and 2.

[0097] The cured films (light-shielding films) obtained by curing the photosensitive resin compositions for black resists of Examples 1 to 5 and Comparative Examples 1 and 2 obtained above were evaluated for the following items, and the results are shown in Table 2.

[0098] [Development characteristic evaluation] (Pattern line width) (Evaluation method) The pattern line width after the main curing (post-baking) was measured with a length measuring microscope "XD-20" (Nikon Corporation) with a mask width of 10 μm. The pattern line width was evaluated in the cases of BT+10 seconds and BT+20 seconds.

[0099] (Evaluation Criteria) ○: Pattern line width is within the range of 10±2 μm ×: Pattern line width is outside the range of 10±2 μm

[0100] (Pattern linearity) (Evaluation method) The 10μm mask pattern after the main curing (post-baking) was observed using an optical microscope. The pattern linearity was evaluated in the cases of BT+10 seconds and BT+20 seconds. A score of △ or higher was considered to be acceptable.

[0101] (Evaluation Criteria) ○: No jagged edges are observed on the pattern edges. △: Jagged edges are observed in some areas of the pattern. ×: Jagged edges of the pattern are observed throughout the entire pattern.

[0102] (Creating a hardened film (light-shielding film) for optical density (OD) evaluation) The photosensitive resin compositions shown in Tables 1 and 2 were preliminarily exposed to a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm 2 The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 nm, so that the film thickness after heat curing would be 1.1 μm, and the coating was prebaked at 90°C for 1 minute using a hot plate to produce a hardened film (light-shielding film). The coating was applied without a negative photomask, and the i-line illuminance was 30 mW / cm. 2 50mJ / cm with ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating the film with ultraviolet light.

[0103] Next, the exposed cured film (light-shielding film) was immersed in a 0.05% potassium hydroxide solution at 25° C. at 1 kgf / cm 2 After developing for 60 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2 The unexposed portions of the cured film (light-shielding film) were removed to form a cured film pattern on the glass substrate, and the cured film was post-baked at 230°C for 30 minutes using a hot air dryer to obtain the cured films (light-shielding films) according to Examples 1 to 5 and Comparative Examples 1 and 2.

[0104] [Optical density evaluation] (Evaluation method) The optical density (OD) of the prepared cured film (light-shielding film) was evaluated using a Macbeth transmission densitometer. In addition, the thickness of the cured film (light-shielding film) formed on the substrate was measured, and the optical density (OD) value was divided by the film thickness to obtain OD / μm.

[0105] The optical density (OD) was calculated using the following formula (1). Optical density (OD)=-log 10 T(1) (T indicates transmittance)

[0106] [Reflectance evaluation] (Evaluation method) For a substrate with a cured film (light-shielding film) prepared in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, the reflectance of each of the cured film (light-shielding film) side and the substrate (glass substrate) side was measured at an incident angle of 2° using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0107] [Table 2]

[0108] It was confirmed that the photosensitive resin compositions for black resists of Examples 1 to 5 had a lower reflectance than a system without silica (Comparative Example 1). Also, it was confirmed that the reflectance was reduced not only on the glass substrate side but also on the coating film (light-shielding film) side compared to a system using solid silica (Comparative Example 2). Also, the cured films (light-shielding films) obtained by curing the photosensitive resin compositions for black resists of Examples 1 to 5 all had good pattern linearity, suggesting that the hollow silica was more uniformly dispersed in the cured film than in a system using solid silica. [Industrial Applicability]

[0109] According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition for black resist having high light-shielding property and low reflectance, and a light-shielding film and a color filter using the same. Furthermore, when the light-shielding film of the present invention is formed on a transparent substrate, it contributes to realizing not only low reflectance on the transparent substrate side but also low reflectance on the coated surface side of the light-shielding film, and is therefore useful as a light-shielding film for sensors of various display devices and solid-state imaging devices.

Claims

1. (A) an unsaturated group-containing photosensitive resin; (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-shielding component selected from a black pigment, a mixed color pigment, and a light-shielding material; (E) silica particles; A photosensitive resin composition for black resist, comprising: The silica particles of the component (E) are hollow particles. Photosensitive resin composition for black resist.

2. A photosensitive resin composition for black resist as described in claim 1, which is a composition for producing a cured film having a thickness of 1.0 to 2.0 μm and an optical density (OD) per μm of 3.6 or more.

3. 2. The photosensitive resin composition for black resist according to claim 1, wherein the unsaturated group-containing photosensitive resin (A) is an unsaturated group-containing photosensitive resin obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol represented by general formula (1) with (meth)acrylic acid, with a polybasic carboxylic acid or an anhydride thereof. 【Chemical 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-, a fluorene-9,9-diyl group represented by general formula (2), or a single bond, and l is an integer of 0 to 10. 【Chemistry 2】

4. 3. The photosensitive resin composition for black resist according to claim 1, wherein the silica particles (E) have an average particle size of 40 to 100 nm.

5. The porosity of the (E) silica particles is 20% by volume or more, The refractive index of the (E) silica particles is 1.10 to 1.

41. The photosensitive resin composition for black resist according to any one of claims 1 to 3.

6. A light-shielding film obtained by curing the photosensitive resin composition for black resist according to any one of claims 1 to 5.

7. A color filter having the light-shielding film according to claim 6 as a black matrix.

Images