Photosensitive resin composition for black resist, light-shielding film, and method for producing light-shielding film for color filter

Abstract

To provide a photosensitive resin composition for a black resist which enables formation of a light-shielding film that has good adhesion to a glass substrate after PCT, has high exposure sensitivity, has good development characteristics, is excellent in volume resistivity and a light-shielding degree, and has a good cross-sectional shape.SOLUTION: A photosensitive resin composition for a black resist contains (a) an alkali-soluble resin, (b) a photopolymerizable compound having an alkylene oxide group or a group having such a structure that lactone is ring-opened, and at least two ethylenically unsaturated bonds, (c) a photopolymerization initiator, (d) a light-shielding agent, and (e) a solvent. The photopolymerizable compound has an acrylic equivalent of 90 g / eq or more and 400 g / eq or less and a molecular weight of 200 or more and 5,000 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition for black resist, a light-shielding film, and a method for producing a light-shielding film for a color filter. [Background technology]

[0002] A color liquid crystal panel has a structure in which a substrate on which a color filter is formed and an opposing substrate (TFT substrate) are bonded together via a sealant, and liquid crystal is filled between the two substrates. A typical method for manufacturing color filters involves forming a black matrix on the surface of a transparent substrate such as glass or a plastic sheet, which serves to improve contrast by suppressing color mixing between the red, green, and blue colors, and then sequentially forming different hues of red, green, and blue, which serve to express all natural colors, in a color pattern such as a stripe or mosaic.

[0003] In recent years, there has been a trend toward narrower frame widths for LCD displays, which reduces the surface area for the sealant used to seal the LCD. This has led to a demand for improved adhesion strength at the interface between the black matrix and the glass substrate. Therefore, it is necessary for the adhesion strength to be maintained even after durability tests (reliability tests), such as the Pressure Cooker Test (PCT). The PCT test involves exposing the LCD panel to harsh conditions of 120°C, 100% humidity, and 2 atm pressure for several hours.

[0004] The black matrix not only improves the contrast of the liquid crystal display, but also functions as an outer frame light-shielding film for the color filter. A portion of the outer frame light-shielding film is bonded to the opposing substrate (glass substrate) via a sealant. Therefore, the black matrix is ​​required to have high adhesive strength with the glass substrate, even when subjected to harsh conditions such as the PCT.

[0005] In recent years, there has been a growing need for higher light-blocking capabilities to improve the visibility of LCD panels. One possible solution to this is to increase the thickness of the black matrix. However, if the thickness is too thick, the film thickness will increase where the black matrix overlaps with the red, green, and blue pixels during the subsequent manufacturing process, resulting in so-called "corner steps." These "corner steps" can disrupt the alignment of the liquid crystal, reducing the panel's visibility. Therefore, there is a need to reduce the thickness of the black matrix and achieve higher light-blocking capabilities.

[0006] Here, if the content of black pigment in the resin composition is increased to achieve a thinner black matrix and higher light-shielding properties, the blending ratio of binder resin, acrylate component, etc., which contribute to curing, becomes relatively small, making it difficult for the coating film to cure sufficiently. As a result, the adhesion between the coating film and the glass substrate decreases, making peeling more likely to occur. Furthermore, if the light-shielding film's light-shielding ability increases, radiation (e.g., ultraviolet light) does not reach the depths of the coating film during exposure. This results in a difference in the way the surface and deeper portions of the coating film cured by exposure shrink during post-baking, making wrinkles more likely to occur on the surface of the light-shielding film. Therefore, if another layer is formed on the surface of the light-shielding film, it raises concerns about not only the adhesion between the light-shielding film and the other layer but also adversely affecting the manufacturing process. As such, in recent years, the demand for adhesion between the black matrix and the substrate has become even more stringent.

[0007] For example, Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble resin having an acryloyl group or an epoxy group, a photopolymerizable compound having a specific structure, and a photopolymerization initiator. Patent Document 1 states that it can provide a photosensitive resin composition that can form a pattern with a good cross-sectional shape, excellent linearity, and excellent adhesion to a substrate. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-212738 Summary of the Invention [Problem to be solved by the invention]

[0009] However, according to the findings of the present inventors, when the pigment concentration of a conventional photosensitive resin composition is increased to, for example, 40% by mass or more, the desired adhesion may not be obtained. Furthermore, the desired patterning properties, such as exposure sensitivity and alkaline developability, may not be obtained. A decrease in developer solubility may affect productivity, such as by reducing yield due to pattern breakage or requiring a long development process.

[0010] An object of the present invention is to provide a photosensitive resin composition for black resist that can form a light-shielding film that has good adhesion to a glass substrate even after PCT, high exposure sensitivity, excellent pattern linearity, volume resistivity, and light-shielding degree, and has a good cross-sectional shape. Another object of the present invention is to provide a method for producing a light-shielding film for a color filter using the photosensitive resin composition, which can shorten the time required for the development step. [Means for solving the problem]

[0011] Therefore, the present inventors have found that by using a photosensitive resin composition containing an alkali-soluble resin, an alkylene oxide group or a group having a structure resulting from the ring-opening of a lactone, and a photopolymerizable compound having at least two ethylenically unsaturated bonds and an acrylic equivalent of 90 g / eq or more and 400 g / eq or less and a molecular weight of 200 or more and 5000 or less, it is possible to form a light-shielding film that exhibits even higher adhesion, has high exposure sensitivity, is excellent in pattern linearity, volume resistivity, and light-shielding degree, and has a good cross-sectional shape, and have thereby completed the present invention.

[0012] The photosensitive resin composition for black resist according to the present invention comprises (a) an alkali-soluble resin, (b) a photopolymerizable compound having an alkylene oxide group or a group having a lactone ring-opened structure and at least two ethylenically unsaturated bonds, (c) a photopolymerization initiator, (d) a light-shielding agent, and (e) a solvent, wherein the component (b) has an acrylic equivalent of 90 g / eq or more and 400 g / eq or less and a molecular weight of 200 or more and 5,000 or less.

[0013] The light-shielding film according to the present invention is obtained by curing the above-mentioned photosensitive resin composition for black resist.

[0014] The method for producing a light-shielding film for a color filter according to the present invention includes a coating film forming step of applying the above-mentioned photosensitive resin composition for a black resist onto a transparent substrate and drying the composition to form a coating film of the photosensitive resin composition for a black resist; an exposure step of irradiating a part of the coating film with radiation through a photomask; a development step of developing the coating film irradiated with radiation and removing the unexposed part; and a heat-curing step of heat-curing the developed coating film. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photosensitive resin composition for black resist that can form a light-shielding film that has good adhesion to a glass substrate even after PCT, high exposure sensitivity, excellent pattern linearity, volume resistivity, and light-shielding degree, and has a good cross-sectional shape. Another object of the present invention is to provide a method for producing a light-shielding film for a color filter using the photosensitive resin composition, which can shorten the time required for the development step. DETAILED DESCRIPTION OF THE INVENTION

[0016] The photosensitive resin composition for black resist of the present invention will be described in detail below.

[0017] The photosensitive resin composition for black resist of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable compound having an alkylene oxide group or a group having a lactone ring-opened structure and at least two ethylenically unsaturated bonds, (c) a photopolymerization initiator, (d) a light-shielding agent, and (e) a solvent.

[0018] 1. Photosensitive resin composition [Component (a)] The component (a) is an alkali-soluble resin. By including the component (a), the photosensitive resin composition can be made soluble in alkaline development.

[0019] The alkali-soluble resin, component (a), preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxy group. Any of these resins can be used without particular limitations. Because the alkali-soluble resin has both a polymerizable unsaturated group and a carboxy group, it acts as a binder and imparts excellent photocurability to the photosensitive resin composition for black resist. It also imparts good developability and patterning properties (pattern line width, pattern linearity), thereby improving the physical properties of the light-shielding film.

[0020] The alkali-soluble resin, component (a) according to this embodiment, is preferably a polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of an epoxy compound having two or more epoxy groups with (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. During the production of the alkali-soluble resin, a polyester is produced by the reaction of a hydroxy group with a polybasic carboxylic acid, and the polyester preferably has a low molecular weight with an average degree of polymerization of about 2 to 500. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group, and refers to either or both of these.

[0021] Examples of the epoxy compound having two or more epoxy groups include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, (o, m, p-) cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, biphenyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having an aromatic structure such as tetrakisphenol ethane type epoxy compounds, and glycidyl polyhydric alcohols. ethers, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate; epoxy compounds having a glycidyl group, such as hydrogenated bisphenol A diglycidyl ether (e.g., Rikaresin HBE-100, manufactured by New Japan Chemical Co., Ltd.; "Rikaresin" is a registered trademark of the company); 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate; 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175, manufactured by Huntsman; "Araldite" is a registered trademark of the company); bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation, "Celloxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,Examples of epoxy compounds include 4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation; "Epolead" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1, manufactured by Shikoku Chemical Industry Co., Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.; "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton.

[0022] Among the above epoxy compounds, bisphenol-type epoxy compounds represented by the following general formula (2), phenol novolac-type epoxy compounds represented by the following general formula (4), and (o, m, p-) cresol novolac-type epoxy compounds are preferred.

[0023] [ka]

[0024] In formula (2), R6 and R7 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a halogen atom; W represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group represented by the following general formula (3), or a single bond; and n is an integer of 0 or more and 10 or less.

[0025] [ka]

[0026] [ka]

[0027] In formula (4), R8~R 11 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 12 ~R 22 independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an alkynyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 9 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and o represents an integer of 1 to 5.

[0028] From the viewpoint of developability and fine line adhesion, the bisphenol type epoxy compound represented by the general formula (2) is more preferred.

[0029] The bisphenol type epoxy compound represented by the general formula (2) is derived from a bisphenol. Examples of the bisphenol 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 -hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5 -dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) )fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]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,Examples of suitable bisphenols include 9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, and 3,3'-biphenol. Among these, bisphenols having a fluorene-9,9-diyl group are preferred from the viewpoint of further improving heat resistance. These bisphenols may be used alone or in combination of two or more.

[0030] Furthermore, the polybasic carboxylic acid or anhydride used to obtain component (a) is preferably a combination of (A) a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof and (B) a tetracarboxylic acid or an acid dianhydride thereof.

[0031] Examples of (A) dicarboxylic acids or tricarboxylic acids or acid monoanhydrides thereof include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic dicarboxylic acids or tricarboxylic acids, aromatic dicarboxylic acids or tricarboxylic acids, or acid monoanhydrides thereof.

[0032] Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include dicarboxylic acids or tricarboxylic acids such as 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, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0033] Examples of the alicyclic dicarboxylic acid or tricarboxylic acid include dicarboxylic acids or tricarboxylic acids such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-3,6-endomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0034] Examples of aromatic dicarboxylic acids or tricarboxylic acids include dicarboxylic acids or tricarboxylic acids such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0035] In the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The above-mentioned dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides may be used alone or in combination of two or more kinds.

[0036] Examples of (B) tetracarboxylic acids or acid dianhydrides thereof include chain hydrocarbon tetracarboxylic acids, alicyclic tetracarboxylic acids, aromatic tetracarboxylic acids, and acid dianhydrides thereof.

[0037] Examples of the chain hydrocarbon tetracarboxylic acid include tetracarboxylic acids such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid, and tetracarboxylic acids having any substituent introduced therein.

[0038] Examples of the alicyclic tetracarboxylic acid include tetracarboxylic acids such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, as well as tetracarboxylic acids having any substituent introduced therein.

[0039] Examples of aromatic tetracarboxylic acids include tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid, as well as tetracarboxylic acids having any substituent introduced therein.

[0040] In the above-mentioned tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. The above-mentioned tetracarboxylic acid or its acid dianhydride may be used alone or in combination of two or more kinds.

[0041] In this case, the molar ratio (A) / (B) of (A) dicarboxylic acid or tricarboxylic acid or its monoanhydride to (B) tetracarboxylic acid or its dianhydride is preferably 0.01 or more and 10.0 or less, more preferably 0.02 or more and less than 3.0. When the molar ratio (A) / (B) is within the above range, an optimal molecular weight can be obtained to obtain a photosensitive resin composition with good photopatterning properties. Note that the smaller the molar ratio (A) / (B), the larger the molecular weight and the lower the alkali solubility tends to be.

[0042] The reaction of the epoxy compound with (meth)acrylic acid and the reaction of the epoxy (meth)acrylate obtained by this reaction with a polybasic acid or its acid anhydride are not particularly limited, and known methods such as those described in JP-A-8-278629 can be used.

[0043] In order to adjust the dissolution rate, the alkali-soluble resin synthesized by the above reaction preferably has a weight-average molecular weight (Mw) of 1,000 to 20,000, more preferably 2,000 to 10,000, and preferably an acid value of 30 mgKOH / g to 200 mgKOH / g. The weight-average molecular weight of the alkali-soluble resin can be determined, for example, using a gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). The acid value can be determined, for example, using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0044] The alkali-soluble resin as component (a) may be used alone or in combination of two or more.

[0045] [(b) Component] The component (b) is a photopolymerizable compound. By including the component (b), it is possible to improve the exposure sensitivity and developability.

[0046] The photopolymerizable compound that is the component (b) according to this embodiment has an alkylene oxide group or a group having a structure in which a lactone ring is opened, and at least two ethylenically unsaturated bonds.

[0047] The photopolymerizable compound (b) preferably has at least one alkylene oxide group having 2 to 6 carbon atoms or a group having a ring-opened structure of a lactone having 2 to 6 carbon atoms (hereinafter simply referred to as a "lactone group"), and more preferably has an alkylene oxide group having 2 to 3 carbon atoms or a lactone group having 4 to 6 carbon atoms. Because the alkylene oxide group or lactone group contains a single-bonded oxygen atom, the lone electron pair of the oxygen atom suppresses steric hindrance, allowing the alkylene oxide group or lactone group to freely rotate within the molecule. This imparts flexibility to the coating film, alleviating internal stresses that arise during thermal curing shrinkage, thereby reducing adhesion after PCT. In particular, lactone groups can have a longer length of consecutive carbon atoms than alkylene oxide groups, making them less hydrophilic and less susceptible to moisture penetration into the coating film, resulting in better adhesion to glass substrates after PCT testing.

[0048] The acrylic equivalent of the photopolymerizable compound is 90 g / eq or more and 400 g / eq or less, preferably 120 g / eq or more and 360 g / eq or less, more preferably 150 g / eq or more and 320 g / eq or less, and even more preferably 190 g / eq or more and 300 g / eq or less. When the acrylic equivalent of the photopolymerizable compound is 400 g / eq or less, the sensitivity to radiation (e.g., ultraviolet light) is high. Furthermore, since the crosslink density is increased, the shrinkage of the coating film itself becomes relatively large, and the light blocking degree per 1 μm of the cured film can be increased. In particular, the smaller the acrylic equivalent, the better the sensitivity. Furthermore, the molecular weight of the photopolymerizable compound is 200 to 5000, preferably 600 to 3500, more preferably 1000 to 1900, and even more preferably 1200 to 1900. When the molecular weight of the photopolymerizable compound is 5000 or less, good solubility in an alkaline developer is obtained, and the compound has appropriate heat sagging properties, so that good pattern properties (e.g., linearity of the pattern) and a good cross-sectional shape can be obtained.

[0049] The acrylic equivalent of the photopolymerizable compound can be determined, for example, by dividing the molecular weight by the number of acrylic functional groups. The weight-average molecular weight (Mw) of the photopolymerizable compound can be determined, for example, using the aforementioned gel permeation chromatography (GPC) "HLC-8220GPC."

[0050] The photopolymerizable compound that is the component (b) according to this embodiment preferably has a structure represented by the following general formula (1).

[0051] [ka]

[0052] In formula (1), Y is independently an alkylene oxide group having 2 to 6 carbon atoms or a structure in which a lactone having 2 to 6 carbon atoms is opened (-C(=O)-(CH2) kIt is a group having a carbon atom number of 2 to 6, and is preferably an alkylene oxide group having 2 to 6 carbon atoms or a group having a structure in which a lactone having 4 to 6 carbon atoms is ring-opened. It is more preferable that at least one of Y is a group having a structure in which a lactone having 6 carbon atoms is ring-opened, and it is even more preferable that all Y are groups having a structure in which a lactone having 6 carbon atoms is ring-opened. a to e are independently integers of 0 to 6, with the proviso that at least one of a to e is an integer of 1 to 6. a to e are preferably 1 or 2. It is preferable that R1 to R5 are independently a group selected from the group consisting of a (meth)acryloyl group and a hydroxy group, and at least two of R1 to R5 are (meth)acryloyl groups. It is preferable that all of R1 to R5 are (meth)acryloyl groups. Z is preferably a group selected from the group consisting of substituted or unsubstituted monovalent to tetravalent hydrocarbon groups, -O- and -S-, more preferably a group selected from the group consisting of substituted or unsubstituted divalent hydrocarbon groups, -O- and -S-, and even more preferably -O-. 1 is independently 0 or 1, preferably 0. m is an integer of 1 to 4, the same as the valence of Z, preferably 2. k is an integer of 1 to 5, preferably 3 to 5. However, when component (b) contains multiple photopolymerizable compounds represented by general formula (1), the photopolymerizable compounds may be the same or different.

[0053] The photopolymerizable compound represented by the above general formula (1) has a large acrylic equivalent compared to a compound not having an alkylene oxide group or a group having a ring-opened lactone structure (e.g., DPHA), but has a long molecular chain and is a polyfunctional acrylate monomer, so that it has good sensitivity to exposure. Furthermore, although the photopolymerizable compound has a relatively large molecular weight, it contains many hydrophilic functional groups such as esters and ethers in the molecule, and therefore has very good solubility in an alkaline developer, allowing for rapid pattern development.

[0054] In addition, since the photopolymerizable compound has a relatively large molecular weight, it is less likely to sag due to heat during post-baking, and can form a pattern with a good cross-sectional shape that maintains its rectangular shape. Furthermore, since the photopolymerizable compound has a lower cross-linking density than a compound that does not have an alkylene oxide group or a group having a lactone ring-opening structure (e.g., DPHA), shrinkage during baking is reduced, and therefore volume resistivity can be increased.

[0055] The photopolymerizable compound represented by the general formula (1) preferably has 2 to 20 (meth)acryloyl groups, more preferably 3 to 10 (meth)acryloyl groups, and even more preferably 3 to 6 (meth)acryloyl groups. When the photopolymerizable compound has two or more (meth)acryloyl groups, the photopolymerizable compound can obtain high sensitivity to radiation (e.g., ultraviolet light). Furthermore, when the number of (meth)acryloyl groups is 20 or less, good patterning characteristics (pattern line width, pattern straightness) can be obtained.

[0056] Specific examples of the photopolymerizable compound represented by the general formula (1) above include ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol hexacaprolactone hexaacrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide-modified triacrylate, and trimethylolpropane ethylene oxide-modified triacrylate (all manufactured by Toagosei Co., Ltd.). Among these, ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol hexacaprolactone hexaacrylate, and dipentaerythritol polycaprolactone hexaacrylate are more preferred. The above photopolymerizable compounds may be used alone or in combination of two or more.

[0057] Component (b) may be a photopolymerizable compound other than the photopolymerizable compound represented by the general formula (1). The photopolymerizable compound may be used in combination with the photopolymerizable compound represented by the general formula (1), or may be used in place of the photopolymerizable compound represented by the general formula (1).

[0058] Examples of photopolymerizable compounds other than the photopolymerizable compound represented by the general formula (1) above include bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified di- and triacrylate, diglycerin ethylene oxide-modified acrylate (all manufactured by Toagosei Co., Ltd.), and alkylene oxide-modified hexa(meth)acrylate of phosphazene.

[0059] [(b') Other photopolymerizable compounds] The photosensitive resin composition of the present invention may contain, as (b') other photopolymerizable compounds, a photopolymerizable compound that does not have an alkylene oxide group or a group having a lactone ring-opened structure. By containing the (b') other photopolymerizable compounds, it is possible to adjust the sensitivity and crosslink density.

[0060] Examples of the (b') other photopolymerizable compound include (meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tetra ... (Meth)acrylic acid esters such as acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate; urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; and compounds having an ethylenic double bond, such as dendritic polymers having a (meth)acrylic group. The above other photopolymerizable compounds may be used alone or in combination of two or more.

[0061] The blending ratio of the above component (a) to the photopolymerizable compound (the sum of the above components (b) and (b')) is preferably 50 / 50 or more and 90 / 10 or less, more preferably 60 / 40 or more and 80 / 20 or less, and even more preferably 60 / 40 or more and 75 / 25 or less, in terms of the weight ratio (a) / ((b)+(b')). When the blending ratio of the above component (a) is 50 / 50 or more, the hardness of the cured film after photocuring is sufficient. In addition, the acid value of the coating film is sufficiently high in the unexposed areas, resulting in good alkaline developability and enabling the formation of linear, sharp patterns in a short period of time. Furthermore, when the blending ratio of the above component (a) is 90 / 10 or less, the proportion of photoreactive functional groups in the resin is sufficient, allowing the formation of the desired crosslinked structure. Furthermore, the acid value of the resin component is appropriate, and the solubility in alkaline developer in the exposed areas is not excessively high, thereby preventing the formed pattern from being thinner than the target line width and preventing pattern loss.

[0062] When the photopolymerizable compound contains (b) a photopolymerizable compound represented by general formula (1) and (b') another photopolymerizable compound, the blending ratio of the component (b) to the component (b') is preferably 15 / 85 or more and 100 / 0 or less, and more preferably 50 / 50 or more and 100 / 0 or less, in terms of weight ratio (b) / (b'). By keeping the weight ratio within this range, the above-mentioned effects of the photopolymerizable compound represented by general formula (1) can be sufficiently obtained.

[0063] [(c) component] Component (c) is a photopolymerization initiator. By including component (c), the reaction in the area irradiated with radiation (e.g., ultraviolet light) proceeds sufficiently, reducing the solubility of the cured area during development, allowing the formation of a desired fine pattern.

[0064] The photopolymerization initiator is not particularly limited as long as it is a compound that has a polymerizable unsaturated bond and can initiate polymerization of an addition-polymerizable compound. Examples of photopolymerization initiators include acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and oxime ester compounds. In the present invention, the photopolymerization initiator is used to include sensitizers.

[0065] Examples of the acetophenone compound include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[0066] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, )-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(pipronyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0067] Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, and the like.

[0068] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

[0069] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

[0070] Examples of the imidazole compound include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0071] Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-acetate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one Oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione 2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O- acetyloxime), 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, etc. The above photopolymerization initiators may be used alone or in combination of two or more.

[0072] In particular, when preparing a photosensitive resin composition containing a high concentration of a light-blocking agent, it is preferable to use O-acyloxime compounds (including ketoximes). Specific examples of this compound group include O-acyloxime photopolymerization initiators represented by general formula (5) or (6). Among these compounds, when using a light-blocking agent at a high pigment concentration or when forming a light-blocking film pattern, it is preferable to use O-acyloxime photopolymerization initiators with a molar absorption coefficient at 365 nm of 10,000 L / mol cm or more.

[0073] [ka]

[0074] In formula (5), R 21 , R 22 are each independently a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R 23is a C1-C15 alkyl group, a C6-C18 aryl group, or a C7-C20 arylalkyl group. Here, the alkyl group and 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 linear, branched, or cyclic.

[0075] [ka]

[0076] In formula (6), R 24 and R 25 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 optionally substituted with an alkyl group having 1 to 6 carbon atoms. 26 are independently a linear 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 be substituted with -O- groups. 24 ~R 26 Some of the hydrogen atoms in the group may be substituted with halogen atoms.

[0077] As the component (c), an active radical generator or an acid generator may be used.

[0078] Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

[0079] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0080] Alternatively, compounds that do not function as photopolymerization initiators or sensitizers by themselves but can enhance their photopolymerization initiator or sensitizer capabilities when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0081] The content of component (c) is preferably 3 to 30 parts by weight, and more preferably 4 to 10 parts by weight, relative to 100 parts by weight of the total of component (a) and components ((b) + (b')). When the content of component (c) is 3 parts by weight or more, the photopolymerization speed is adequate, ensuring sufficient sensitivity. Furthermore, when the content of component (c) is 30 parts by weight or less, the line width can be faithfully reproduced on the mask, and the pattern edge can be sharpened.

[0082] [(d) component] The component (d) is a light-blocking agent. By including the component (d), the light-blocking properties of the color filter can be sufficiently obtained.

[0083] As the light-shielding agent, which is the component (d) according to this embodiment, a black pigment or a mixed-color organic pigment can be used.

[0084] Examples of black pigments include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, chromium oxide, and iron oxide.

[0085] Examples of mixed-color organic pigments include those that are pseudo-blackened by mixing at least two colors 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.

[0086] The component (d) may be used alone or in combination of two or more types depending on the desired function of the photosensitive resin composition.

[0087] 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 with 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.

[0088] Among the above light-shielding agents, carbon black, which is a black pigment, is preferred because of its excellent light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins.

[0089] The blending ratio of component (d) can be determined arbitrarily depending on the desired light-blocking degree, but is preferably 30% by mass or more and 60% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and even more preferably 45% by mass or more and 60% by mass or less, based on the solid content of the photosensitive resin composition. When the light-blocking agent is 30% by mass or more based on the solid content of the photosensitive resin composition, sufficient light-blocking properties can be obtained. When the light-blocking agent is 60% by mass or less, a sufficient amount of photosensitive resin is contained, thereby achieving the desired development characteristics and film-forming ability.

[0090] The component (d) is usually dispersed in a dispersion medium and mixed with other formulation components as a light-shielding component dispersion, and a dispersant may be added in this case. The dispersant may be any known compound used for dispersing pigments (light-shielding components) (e.g., compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion promoters, etc.) and the like, without any particular limitation.

[0091] Examples of the dispersion medium include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and the like.

[0092] Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing 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, or a primary, secondary, or tertiary amino group, as an adsorption site for the colorant, an amine value of 1 mgKOH / g to 100 mgKOH / g, and a number-average molecular weight (Mn) of 1,000 to 100,000. The blending amount of this dispersant is preferably 1% to 35% by weight, more preferably 2% to 25% by weight, of the light-blocking component. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those without dispersion-promoting properties are not considered dispersants. However, this does not limit their use for the purpose of stabilizing dispersion.

[0093] [(e) component] Component (e) is a solvent. By including component (e), a liquid photosensitive resin composition containing the above-mentioned components (a) to (d) can be obtained.

[0094] Examples of component (e) 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; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of the component (e) 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. One type of component (e) may be used alone, or two or more types may be used in combination.

[0095] The content of component (e) varies depending on the target viscosity, but is preferably 70% by mass or more and 90% by mass or less relative to the total mass of the photosensitive resin composition. When the content of component (e) is 70% by mass or more, the viscosity can be made to be easy to apply the photosensitive resin composition onto a substrate, and when it is 90% by mass or less, the time required for drying the photosensitive resin composition after application onto a substrate can be shortened.

[0096] [Surfactants] The photosensitive resin composition for black resist according to the present invention may contain a surfactant from the viewpoint of smoothness of the light-shielding film and suppression of Benard cell.

[0097] Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolinium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, silicone surfactants having a polydimethylsiloxane or the like as a main skeleton, fluorine-based surfactants, etc. The above surfactants may be used alone or in combination of two or more.

[0098] The content of the surfactant is preferably 0.001% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less, based on the total mass of the solid content. When the content of the surfactant is 0.001% by mass or more, based on the total mass of component (a), the desired smoothness of the light-shielding film can be achieved and Benard cells can be suppressed. When the content is 5% by mass or less, good coating film properties can be obtained.

[0099] [Coupling agent] The photosensitive resin composition for black resist according to the present invention may contain a silane coupling agent from the viewpoint of improving adhesion between the glass surface and the cured film through chemical bonding.

[0100] The silane coupling agent preferably has a reactive group such as an amino group, an isocyanate group, a ureido group, an epoxy group, a vinyl group, a (meth)acrylic group, or a mercapto group, and more preferably has an epoxy group, an isocyanate group, or a methacryl group. Specific examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0101] The content of the silane coupling agent is preferably 0.3% by mass or more and 2% by mass or less, more preferably 0.7% by mass or more and 1.4% by mass or less, based on the solid content of the photosensitive resin composition. When the content of the silane coupling agent is 0.3% by mass or more, sufficient adhesion can be obtained between the glass substrate and the cured film. When the content of the silane coupling agent is 2% by mass or less, the generation of aggregated foreign matter can be suppressed.

[0102] [Other ingredients] The photosensitive resin composition for black resist according to the present invention may contain additives such as other resin components, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, antifoaming agents, viscosity modifiers, and ultraviolet absorbers, as required.

[0103] Examples of other resin components include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, and epoxy resins.

[0104] Examples of epoxy resins include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jERYX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, and the like. esters, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate; epoxy compounds having a glycidyl group, such as hydrogenated bisphenol A diglycidyl ether (e.g., Rikaresin HBE-100, manufactured by New Japan Chemical Co., Ltd.; "Rikaresin" is a registered trademark of the company); 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175, manufactured by Huntsman; "Araldite" is a registered trademark of the company); bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation, "Celloxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,Examples of epoxy compounds include 4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation; "Epolead" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1, manufactured by Shikoku Chemical Industry Co., Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.; "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton.

[0105] Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complex compounds, and the like, which contribute to the curing of epoxy resins.

[0106] Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, and the like, which contribute to accelerating the curing of epoxy resins.

[0107] Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

[0108] Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of the filler include glass fiber, silica, mica, alumina, etc.

[0109] Examples of the leveling agent and defoaming agent include silicone-based, fluorine-based, and acrylic-based compounds.

[0110] The photosensitive resin composition for black resist of the present invention can be obtained by mixing the above-mentioned components (a) to (e) and the optional component (b').

[0111] The photosensitive resin composition for black matrix of the present invention preferably contains the above components (a) to (d) and optional component (b') in a total amount of 80 mass % or more, and more preferably 90 mass % or more, of the solid content excluding the solvent (the solid content includes monomers that become solid after curing).

[0112] The photosensitive resin composition for black resist of the present invention has good adhesion to glass substrates even after PCT, has high exposure sensitivity, and is capable of forming a light-shielding film that is excellent in pattern linearity, volume resistivity, and light-shielding degree, and that has a good cross-sectional shape.

[0113] 2. Manufacturing method of light-shielding film for color filters A method for manufacturing the light-shielding film for a color filter will be described below.

[0114] The method for producing a light-shielding film for a color filter according to the present invention includes: (1) a coating film forming step of applying the above-mentioned photosensitive resin composition for black resist onto a transparent substrate and drying the composition to form a coating film of the photosensitive resin composition for black resist, (2) an exposure step of irradiating a part of the coating film with radiation through a photomask, (3) a development step of developing the irradiated coating film and removing the unexposed part, and (4) a heat curing step of heat curing the developed coating film. Each step will be described below.

[0115] [Coating film formation process] The coating film forming step is a step of applying the above-mentioned photosensitive resin composition for black resist onto a substrate and drying it to form a coating film.

[0116] The substrate may be a known one, and examples of the substrate include a glass substrate, a silicon wafer, and a plastic substrate (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, etc.) on which a transparent electrode such as ITO or gold is vapor-deposited or patterned.

[0117] The photosensitive resin composition can be applied by a known application method. Examples of the application method include a known solution immersion method, a spray method, and methods using a roller coater, a land coater, a slit coater, or a spinner. By using these methods, the photosensitive resin composition can be applied to a desired thickness.

[0118] The photosensitive resin composition applied by the above method can be dried by a known drying method. The drying method can be performed by heating with an oven, a hot air blower, a hot plate, an infrared heater, or the like, vacuum drying, or a combination of these. The heating temperature and heating time of the resin film can be appropriately selected depending on the solvent used. The heating temperature and heating time can be appropriately selected depending on the solvent used, and are preferably performed, for example, at 60 to 110°C for 1 to 5 minutes.

[0119] [Exposure process] The exposure step is a step in which a part of the coating layer is irradiated with radiation through a photomask to photocure the part of the coating (photosensitive resin composition) corresponding to the pattern.

[0120] A known photomask can be used as the photomask. Examples of photomasks include multi-tone masks such as half-tone masks and gray-tone masks. A gray-tone mask has a light-shielding portion and a diffraction grating formed on a light-transmitting substrate. The diffraction grating has light-transmitting regions such as slits, dots, and meshes spaced at intervals equal to or less than the resolution limit of the light used for exposure, and this configuration controls the light transmittance. A half-tone mask has a light-shielding portion and a semi-transmitting portion formed on a light-transmitting substrate. The semi-transmitting portion controls the transmittance of the light used for exposure.

[0121] In the exposure step, the exposure device and the exposure irradiation conditions can be selected appropriately. Examples of the radiation to be irradiated include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among the above-mentioned radiation, ultraviolet light is preferred. Furthermore, known exposure devices (ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, far ultraviolet lamps, etc.) can be used as the device for irradiating the radiation. Furthermore, the wavelength of the irradiated radiation is preferably 250 nm or more and 400 nm or less. The radiation exposure dose is 25 mJ / cm. 2 More than 3000mJ / cm 2 It is preferable that:

[0122] [Development process] The development step is a step in which the irradiated coating film is developed with an alkali to remove the unexposed areas of the coating film.

[0123] Examples of the developing method for the coating film include shower developing, spray developing, dip (immersion) developing, puddle (puddle) developing, etc. The above developing methods can be carried out using a commercially available developing machine, ultrasonic cleaner, etc.

[0124] Examples of developers suitable for development include aqueous solutions of alkali metal or alkaline earth metal carbonates, and aqueous solutions of alkali metal hydroxides. Among these, it is preferable to use a weakly alkaline aqueous solution containing 0.05 to 3 mass % of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate at a temperature of 23 to 28° C. In addition, a commercially available developing machine, ultrasonic cleaner, or the like can be used in the development step.

[0125] [Heat curing process] The heat curing step is a step in which the exposed area (coating film) after development is heat treated to completely cure (post-bake).

[0126] The exposed area (coating film) after development can be heated by a known method (heating with an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying, or a combination of these). The heating temperature is not particularly limited as long as it is a temperature at which the coating film is fully cured (post-baked). The heating temperature is preferably 180 to 250°C for 20 to 60 minutes.

[0127] The method for producing a light-shielding film for a color filter of the present invention uses the photosensitive resin composition for a black resist of the present invention, which has good developability, and therefore the time required for the development step can be shortened.

[0128] 3. Light-shielding film The light-shielding film of the present invention is obtained by curing the above-mentioned photosensitive resin composition for black matrix. The light-shielding film of the present invention enables high light-shielding of liquid crystal panels. Furthermore, it can be applied to liquid crystal displays with narrow frames. [Example]

[0129] Hereinafter, the embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0130] First, synthesis examples of alkali-soluble resins, which are component (a) of the present invention, will be described. Unless otherwise specified, the resins in the synthesis examples were evaluated as follows.

[0131] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place onwards. In the examples, all glass substrates used to prepare the cured film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0132] [Solid content concentration] The solids concentration was calculated from the following formula using the weight [W1(g)] of 1 g of the resin solution obtained in the synthesis example impregnated into a glass filter [weight: W0(g)] and the weight [W2(g)] after heating at 160°C for 2 hours. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0133] [Acid value] The acid value was determined by dissolving the resin solution in dioxane and titrating it with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0134] [Molecular weight] The molecular weight was measured 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).

[0135] [Acrylic equivalent] The acrylic equivalent weight was determined by dividing the molecular weight by the number of acrylic functional groups.

[0136] The abbreviations used in the synthesis examples are as follows. BPFE: bisphenol fluorene type epoxy resin (an epoxy compound in which W in the compound of general formula (2) is a fluorene-9,9-diyl group, R6 and R7 are hydrogen, and n is 0 to 0.15) AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0137] [Synthesis Example 1] A 500 mL four-neck flask equipped with a reflux condenser was charged with BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) 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 alkali-soluble resin solution (a). The solids concentration of the resin solution was 56.5% by mass, the acid value (solids equivalent) was 103 mg KOH / g, and the Mw by GPC analysis was 3600.

[0138] [Synthesis Example 2] (Other photopolymerizable compounds) PTMA (20 g, 0.19 mol of mercapto groups), DPHA (212 g (2.12 mol of acrylic groups)), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added to a 1 L four-neck flask and reacted at 60°C for 12 hours to obtain dendritic polymer solution (b')-2. The solids concentration of the dendritic polymer solution was 80% by mass, and the Mw value determined by GPC analysis was 10,000. The disappearance of the mercapto groups from the resulting dendritic polymer was confirmed by iodometry.

[0139] Photosensitive resin compositions for black resists in Examples 1 to 9 and Comparative Examples 1 and 2 were prepared in the amounts (unit: mass %) shown in Table 1. The ingredients used in Table 1 are as follows. The amounts of (a) to (d), (b') and dispersant in Table 1 represent the amount of solid content only.

[0140] (alkali-soluble resin) (a): Resin obtained in Synthesis Example 1

[0141] (Photopolymerizable compound) (b)-1: Ethylene oxide-modified dipentaerythritol hexaacrylate (KAYARAD DPEA-12, acrylic equivalent 185 g / eq, molecular weight 1107) (b)-2: Dipentaerythritol hexacaprolactone hexaacrylate (KAYARAD DPCA-60, acrylic equivalent 211 g / eq, molecular weight 1263) (b)-3: Dipentaerythritol polycaprolactone hexaacrylate (KAYARAD DPCA-120, acrylic equivalent 325 g / eq, molecular weight 1948)

[0142] The photopolymerizable compounds (b)-1 to (b)-3 are all manufactured by Nippon Kayaku Co., Ltd., and "KAYARAD" is a registered trademark of the same company.

[0143] (Other photopolymerizable compounds) (b')-1: Dipentaerythritol penta / hexaacrylate mixture (KAYARAD DPHA, acrylic equivalent 97 g / eq, molecular weight 578, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is a registered trademark of the company) (b')-2: Resinous polymer obtained in Synthesis Example 2 above

[0144] (Photopolymerization initiator) (c): Irgacure OXE02 (manufactured by BASF Japan Ltd., "Irgacure" is a registered trademark of the company)

[0145] (Light-blocking component) (d): Carbon black and polymer dispersant

[0146] (solvent) (e)-1: Propylene glycol monomethyl ether acetate (e)-2: Diethylene glycol dimethyl ether (e)-3: Diethylene glycol ethyl methyl ether

[0147] [Table 1]

[0148] [evaluation] (Preparation of substrate with cured film (coating film) for adhesion strength evaluation) The photosensitive resin composition for black resist shown in Table 1 was applied to a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing would be 1.1 μm, and the substrate was prebaked on a hot plate at 90°C for 1 minute to produce a hardened film (coated film). Next, without using a negative photomask, the substrate was exposed to an i-line illuminance of 30 mW / cm. 2 Ultra-high pressure mercury lamp, 100mJ / cm 2 The cured film (coating film) after exposure was post-baked at 230°C for 30 minutes using a hot air dryer to obtain a substrate with a cured film (coating film) for evaluation of adhesion strength.

[0149] [Adhesion strength (seal strength) evaluation] (Evaluation method) The test was carried out in accordance with the three-point bending adhesion test method of JIS K6856-1994.

[0150] Specifically, the substrate with the cured film (coating) and a glass substrate not coated with the photosensitive resin composition shown in Table 1 (hereinafter also referred to as the "uncoated substrate") were each cut into 20 mm x 63 mm strips to prepare test specimens. The substrate with the cured film (coating) and the uncoated substrate were then overlapped with a certain amount of sealant interposed between them, and the two substrates (test specimens) were bonded together to a width of 8 mm. The shape of the sealant when overlapped was a circle with a diameter of approximately 5 mm. The overlapped test specimens were then prebaked at 90°C for 20 minutes and then postbaked at 150°C for 2 hours to prepare three-point bending test specimens. A pressure cooker test (PCT) was then performed under conditions of 100% RH, 2 atm, and 121°C for 5 hours.

[0151] The three-point bending test is carried out as follows: The test piece obtained above is supported by two supports (the distance between the two supports is 3 cm) so that the overlapping portion is at the center, and a load is applied from directly above the overlapping portion to directly below using a tensile tester "Tensilon UCT-100" (manufactured by Orientec Co., Ltd.) at a rate of 1 mm / min. The peeled surface is observed and the load at that time is read, and this value is divided by the area of ​​the applied sealant to determine the load per unit area as the adhesion strength.

[0152] (Evaluation criteria) ◎: Adhesion strength after PCT is 30kgf / cm 2 That's all ○: Adhesion strength after PCT is 10kgf / cm 2 More than 30kgf / cm 2 is less than ×: Adhesion strength after PCT is 10 kgf / cm 2 is less than

[0153] (Preparation of substrates with cured film (coating film) for evaluating pattern line width, pattern linearity, and taper angle) The photosensitive resin composition for black resist shown in Table 1 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after heat curing would be 1.1 μm, and the substrate was prebaked at 90°C for 1 minute. After that, the exposure gap was adjusted to 100 μm, and a negative photomask with 10 μm stripes was placed on the dried coating film, and the black resist was exposed to light from an ultra-high pressure mercury lamp (wavelength 365 nm, i-line illuminance 30 mW / cm). 2 ) at 100mJ / cm 2 The photosensitive portion was exposed to ultraviolet light to cause a photo-curing reaction (exposure).

[0154] Next, the exposed cured film (coating film) was soaked in a 0.05% aqueous potassium hydroxide solution at 23°C under a pressure of 1 kgf / cm 2 After developing for 20 seconds after dissolution, the pressure was increased to 5 kgf / cm 2 The developed cured film (coating film) was then post-cured (post-baked) using a hot air dryer at 230°C for 30 minutes to obtain a substrate with a cured film (coating film) for evaluation of pattern line width, pattern linearity, and taper angle.

[0155] [Dissolution time] (Evaluation method) The development was carried out under the above conditions while checking the state of the developed substrate, and the film dissolution time [s] was measured. The dissolution time was the time when the glass substrate in the unexposed area of ​​the black film was exposed.

[0156] (Evaluation criteria) Good: Dissolution time is less than 25 seconds △: Dissolution time is 25 seconds or more but less than 40 seconds ×: Dissolution time is 40 seconds or more

[0157] [Pattern line width evaluation] (Evaluation method) After main curing (post-baking), the pattern line width [μm] of a mask width of 10 μm was measured using a length measuring microscope "XD-20" (Nikon Corporation).

[0158] (Evaluation criteria) ○: Pattern line width is 10 μm or more △: Pattern line width is 8 μm or more and less than 10 μm ×: Pattern line width is less than 8 μm

[0159] [Pattern linearity evaluation] (Evaluation method) The 10 μm mask pattern after main curing (post-baking) was observed using an optical microscope.

[0160] (Evaluation criteria) ○: No jagged edges are observed on the pattern edges △: Slight jaggedness is observed on the pattern edge ×: Jagged edges of the pattern are observed

[0161] [Taper angle] (Evaluation method) The taper angle [°] of a mask width of 10 μm was measured using a scanning electron microscope (SEM) "VE-7800" (manufactured by Keyence Corporation).

[0162] (Evaluation criteria) ○: Taper angle is 55° or more △: Taper angle is 30° or more and less than 55° ×: Taper angle is less than 30°

[0163] [Volume resistivity] (Evaluation method) The photosensitive resin composition for black resist was applied to a 100 mm × 100 mm chrome-deposited substrate (manufactured by Technoprint Co., Ltd.) using a spin coater so that the film thickness after post-baking would be 3.0 μm, and the substrate was pre-baked at 90°C for 1 minute. Thereafter, the composition was pre-baked at 100 mJ / cm without using a negative photomask. 2 The substrate was then post-baked at 230°C for 180 minutes using a hot air dryer. After post-baking, aluminum terminals were attached to the substrate, and the volume resistivity [Ω·cm] of the cured film (coating film) was measured using a volume resistivity meter "6517A" (manufactured by Keithley Instruments Inc.).

[0164] (Evaluation criteria) ○: The volume resistivity is 12 or more (1.0×10^12 Ω·cm) when an applied voltage of 10V is used. ×: The volume resistivity is less than the 12th power (1.0×10^12 Ω·cm) when an applied voltage of 10V is used.

[0165] The evaluation results are shown in Table 2.

[0166] [Table 2]

[0167] The light-shielding films (coatings) obtained from the photosensitive resin compositions of Examples 1 to 9 showed good results in the evaluation of adhesion strength after PCT. In particular, the photosensitive resin compositions of Examples 2 to 9, which contained photopolymerizable compounds having lactone groups, showed extremely good results in the evaluation of adhesion strength. The reason for the improved adhesion is thought to be that, as described above, ethylene oxide groups and lactone groups contain single-bonded oxygen atoms, which impart flexibility to the coating film and alleviate the internal stress of the coating film that occurs during thermal curing shrinkage. Furthermore, lactone groups can have a longer length of continuous carbon atoms than alkylene oxide groups, which is thought to reduce hydrophilicity and make it more difficult for moisture to penetrate into the coating film.

[0168] Furthermore, the photosensitive resin compositions of Examples 1 to 9 also achieved favorable results in terms of pattern linearity, dissolution time, taper angle, and volume resistivity. The reason for the improved pattern linearity is believed to be that although the acrylic equivalent of the photopolymerizable compound (b) is larger than that of compounds lacking an alkylene oxide group or lactone group, it has a long molecular chain and is a polyfunctional acrylate monomer, resulting in high sensitivity to light exposure. The reason for the improved dissolution time is believed to be that despite the relatively large molecular weight of the photopolymerizable compound, it contains many hydrophilic functional groups such as esters and ethers, thereby improving its solubility in alkaline developers. The reason for the increased taper angle is believed to be that the relatively large molecular weight of the photopolymerizable compound makes it less susceptible to thermal sagging during post-baking. The reason for the improved volume resistivity is believed to be that the crosslinking density is smaller than that of photopolymerizable compounds lacking an alkylene oxide group or lactone group, resulting in reduced shrinkage during baking.

[0169] When a liquid crystal panel was fabricated using a color filter having a black matrix formed using the photosensitive resin compositions of Examples 1 to 9, there was almost no peeling of the black matrix even under severe conditions, and leakage of liquid crystal was prevented. Furthermore, a light-shielding film with a high taper angle was obtained by curing the photosensitive resin composition without sacrificing pattern characteristics (pattern linearity, etc.). Furthermore, a positive effect of shortening development time was obtained during manufacturing. Therefore, even when fabricating a black matrix with a high light-shielding rate or a narrow adhesive area, peeling of the coating film from the glass substrate is reduced, ensuring high productivity (yield) and reliability. [Industrial Applicability]

[0170] The photosensitive resin composition for black resist of the present invention can provide a photosensitive resin composition for black resist that has high adhesion to glass substrates even after PCT, high exposure sensitivity, and is capable of forming a light-shielding film that is excellent in pattern linearity, volume resistivity, and light-shielding degree, and has a good cross-sectional shape. Furthermore, use of the photosensitive resin composition for black resist of the present invention can shorten the time required for the development process. The photosensitive resin composition for black resist of the present invention can obtain the necessary adhesion strength even with a small adhesion area, thereby enabling the frame area of ​​displays to be narrowed. This contributes to the design and miniaturization of devices.

Claims

1. (a) an alkali-soluble resin; (b) dipentaerythritol hexacaprolactone hexaacrylate; and (c) a photopolymerization initiator containing an oxime ester compound; (d) a light-blocking agent; and (e) a solvent; a photosensitive resin composition for black resist, which is applied to a transparent substrate, dried on the transparent substrate, and then exposed to light on the same transparent substrate to be cured, thereby forming a cured product that is in close contact with the transparent substrate; The component (a) is a polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of a bisphenol-type epoxy compound represented by the following general formula (2) with (meth)acrylic acid with a polybasic carboxylic acid or an anhydride thereof: 【Chemical 1】 (In formula (2), R ６ and R ７ are independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a halogen atom; W 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 the following general formula (3), or a single bond, provided that at least one of W is a fluorene-9,9-diyl group represented by the general formula (3), and n is an integer of 0 or more and 10 or less. 【Chemistry 2】 Photosensitive resin composition for black resist.

2. A light-shielding film obtained by curing the photosensitive resin composition for black resist according to claim 1.

3. a coating film forming step of applying the photosensitive resin composition for black resist according to claim 1 onto a transparent substrate and drying the composition to form a coating film of the photosensitive resin composition for black resist; an exposure step of irradiating a portion of the coating film on the transparent substrate with radiation through a photomask; a developing step of developing the radiation-irradiated coating film on the transparent substrate to remove unexposed portions; a heat curing step of heat curing the developed coating film on the transparent substrate; and forming a cured product in close contact with the transparent substrate.

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