Photosensitive resin composition, light-shielding film, color filter, touch panel and display device

Abstract

To provide a photosensitive resin composition from which a light-shielding film having both low reflectivity and good developability can be obtained.SOLUTION: A photosensitive resin composition contains (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable compound having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from the group consisting of a black pigment and a mixed color pigment, (E) inorganic fine particles having a refractive index of 1.10 to 1.80, and (F) a solvent, wherein (F) the solvent contains a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent (excluding propylene glycol monomethyl ether acetate) having ΔEST of 0.45 eV or more, and a content mass of the second solvent is 4.0% to 60.0% with respect to the total mass of (F) the solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a light-shielding film formed from the photosensitive resin composition, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or the touch panel. [Background technology]

[0002] In recent years, with the development of mobile terminals, there has been an increase in display devices having touch panels, liquid crystal panels, organic electroluminescence (EL) panels, etc., for use outdoors or in vehicles. In such display devices, the touch panel may be provided with a black matrix on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back. The liquid crystal panel may be provided with a black matrix to suppress light leakage from the screen when black is displayed and to suppress color mixing between adjacent color resists. The organic EL panel may be provided with an overcoat layer that can impart appropriate light-blocking properties, transmitting light emitted by the organic EL while blocking light reflected by the organic EL panel when external light enters the organic EL display device.

[0003] These light-shielding films such as black matrices and overcoat layers are required to have low reflectance and, since they may be patterned depending on the application, they are also required to have developability. For example, Patent Document 1 describes a photosensitive resin composition containing carbon black, hydrophobic silica fine particles dispersed in a specific urethane-based dispersant, and an alkali-soluble resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-161815 Summary of the Invention [Problem to be solved by the invention]

[0005] However, according to the findings of the present inventors, the light-shielding film formed from the photosensitive resin composition described in Patent Document 1 has a problem in that it is unable to achieve both low reflectivity and good developability.

[0006] The present invention has been made in view of the above points, and aims to provide a photosensitive resin composition that can achieve both low reflectivity and good developability, a light-shielding film formed from the photosensitive resin composition, a color filter and a touch panel that have the light-shielding film, and a display device that has the color filter or the touch panel. [Means for solving the problem]

[0007] One aspect of the present invention for solving the above problems relates to the following photosensitive resin compositions [1] to [4].

[0008] [1] (A) an unsaturated group-containing alkali-soluble resin; (B) a photopolymerizable compound having at least two unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-blocking component selected from the group consisting of black pigments and mixed-color pigments; (E) inorganic fine particles having a refractive index of 1.10 to 1.80; (F) solvent and Including, The (F) solvent is a first solvent which is propylene glycol monomethyl ether acetate, and a ΔE ST and a second solvent (excluding propylene glycol monomethyl ether acetate) having a VI of 0.45 eV or more, The content by mass of the second solvent is 4.0% to 60.0% based on the total mass of the (F) solvent. Photosensitive resin composition.

[0009] [2] The (E) inorganic fine particles are silica particles. [1] The photosensitive resin composition according to [1].

[0010] [3] The (E) inorganic fine particles have an average primary particle diameter of 1 nm to 100 nm. The photosensitive resin composition according to [1] or [2].

[0011] [4] The second solvent contains a solvent represented by the following general formula (F-2): The photosensitive resin composition according to any one of [1] to [3].

[0012] [ka]

[0013] In the general formula (F-2), R a represents an alkyl group having 1 to 4 carbon atoms.

[0014] One aspect of the present invention for solving the above problems relates to the following light-shielding film [5].

[0015] [5] A light-shielding film formed from the photosensitive resin composition according to any one of [1] to [4].

[0016] One aspect of the present invention for solving the above problems relates to the following color filter [6].

[0017] [6] A color filter having the light-shielding film according to [5].

[0018] One aspect of the present invention for solving the above problem relates to a touch panel as described below in [7].

[0019] [7] A touch panel having the light-shielding film according to [5].

[0020] One aspect of the present invention for solving the above problems relates to the following display devices [8] and [9].

[0021] [8] A display device having the color filter according to [6].

[0022] [9] A display device having the touch panel described in [7]. [Effects of the Invention]

[0023] According to the present invention, there are provided a photosensitive resin composition that can achieve both low reflectivity and developability, a light-shielding film formed from the photosensitive resin composition, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or the touch panel. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0025] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0026] The present invention will be described in detail below.

[0027] 1. Photosensitive resin composition The photosensitive resin composition according to this embodiment comprises: (A) an unsaturated group-containing alkali-soluble resin (hereinafter also referred to simply as "component (A)"), (B) a photopolymerizable compound having at least two unsaturated bonds (hereinafter also referred to simply as "component (B)"); (C) a photopolymerization initiator (hereinafter also referred to simply as "component (C)"); (D) at least one light-shielding component selected from the group consisting of black pigments and mixed color pigments (hereinafter also referred to simply as "component (D)"); (E) inorganic fine particles having a refractive index of 1.10 to 1.80 (hereinafter also referred to simply as "component (E)"); (F) Solvent (hereinafter simply referred to as "Component (F)") Including, The component (F) is a first solvent which is propylene glycol monomethyl ether acetate, and a ΔE ST and a second solvent (excluding propylene glycol monomethyl ether acetate) having a VI of 0.45 eV or more, The content by mass of the second solvent is 4.0% to 60.0% based on the total mass of the component (F).

[0028] Each component will be explained below.

[0029] 1-1. (A) Unsaturated group-containing alkali-soluble resin Component (A) contains a polymerizable unsaturated group, which provides the photosensitive resin composition with excellent photocurability, and upon curing, its molecular weight increases, allowing it to function as a binder. Component (A) also contains an acidic group, which provides good developability.

[0030] Component (A) is a resin having a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility, and any such resin can be used without any particular limitation.

[0031] The polymerizable unsaturated group contained in the component (A) is not particularly limited as long as it is a functional group containing an unsaturated bond, but is preferably a (meth)acryloyl group.

[0032] Examples of the acidic group contained in the component (A) for imparting alkali solubility include a carboxy group, a phosphate group, a sulfonic acid group, etc. From the viewpoint of easily improving developability, a carboxy group is preferred.

[0033] Component (A) is preferably an 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 unsaturated group-containing alkali-soluble resin, a polyester is produced by the reaction of a hydroxy group with a polybasic carboxylic acid. Component (A) is preferably a low-molecular-weight resin in which the average degree of polymerization of the polyester is approximately 2 to 500. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and "(meth)acrylate" is a general term for acrylate and methacrylate, and each refers to one or both of these.

[0034] 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 (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having an aromatic structure such as tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, (meth)acrylates containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, copolymers of monomers having a methyl group, 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 Chemical Co., Ltd., "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128, manufactured by The 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.

[0035] Examples of the component (A) include alkali-soluble resins that are acrylic copolymers as described below.

[0036] Examples of the acrylic copolymer include a copolymer of (meth)acrylic acid, a (meth)acrylic acid ester, etc., and a resin having a (meth)acryloyl group and a carboxy group. Examples of the resin include an alkali-soluble resin containing a polymerizable unsaturated group, which is obtained by copolymerizing a (meth)acrylic acid ester containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymer include a copolymer disclosed in Japanese Patent Application Laid-Open No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the 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 which has a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH / g; and a polymerizable unsaturated group-containing alkali-soluble resin disclosed in Japanese Patent Application Laid-Open No. 2018-141968, which is a polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, and which includes units derived from (meth)acrylic acid ester compounds and units having a (meth)acryloyl group and a di- or tricarboxylic acid residue.

[0037] From the viewpoint of enhancing alkali resistance after photocuring and facilitating the improvement of developability of the light-shielding film, it is preferable that component (A) has at least one aromatic ring and alicyclic structure in the molecule. Furthermore, component (A) more preferably has multiple aromatic rings, is further preferably an alkali-soluble resin having a repeating unit containing a fluorene structure, and is most preferably an alkali-soluble resin having a repeating unit containing a bisarylfluorene skeleton represented by the following general formula (A-1):

[0038] [ka]

[0039] In formula (A-1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a (meth)acryloyl group or a substituent represented by the following general formula (A-2) or the following general formula (A-3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by the following general formula (A-4), and at least one Z is a substituent represented by the following general formula (A-4). n is a number with an average value of 1 to 20.

[0040] [ka]

[0041] [ka]

[0042] In formulas (A-2) and (A-3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site.

[0043] [ka]

[0044] In formula (A-4), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0045] Furthermore, Y in the general formula (A-1) preferably contains at least one aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include a phenyl group, a biphenyl group, a benzophenone group, a naphthalene group, and a biphenyl ether group. Among the aromatic hydrocarbon groups, a biphenyl group, a benzophenone group, or a naphthalene group is preferred. When Y is an aromatic hydrocarbon group, the alkali resistance of the cured film can be improved.

[0046] Next, a method for producing the unsaturated group-containing alkali-soluble resin (A) represented by the above general formula (A-1) will be described in detail.

[0047] First, an epoxy compound (a-1) (hereinafter simply referred to as "epoxy compound (a-1)") having a bisarylfluorene skeleton represented by the following general formula (A-5), which may have several oxyalkylene groups per molecule, is reacted with at least one of (meth)acrylic acid and (meth)acrylic acid derivatives represented by the following general formula (A-6) and the following general formula (A-7) to obtain a diol compound that is an epoxy (meth)acrylate. The bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

[0048] [ka]

[0049] In formula (A-5), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3.

[0050] [ka]

[0051] [ka]

[0052] In formulas (A-6) and (A-7), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.

[0053] The reaction of the epoxy compound (a-1) with the (meth)acrylic acid or (meth)acrylic acid derivative can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 discloses that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. In this embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by formula (A-8) (hereinafter, also simply referred to as "diol (d) represented by general formula (A-8)").

[0054] [ka]

[0055] In formula (A-8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each G is independently a (meth)acryloyl group or a substituent represented by the following general formula (A-2) or general formula (A-3). Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3.

[0056] [ka]

[0057] [ka]

[0058] In formulas (A-2) and (A-3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site.

[0059] In the synthesis of the diol (d) represented by general formula (A-8) and the subsequent production of the unsaturated group-containing alkali-soluble resin represented by general formula (A-1) by reacting it with a polycarboxylic acid or an anhydride thereof, the reaction is usually carried out in a solvent using a catalyst as necessary.

[0060] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Note that there are no particular restrictions on the reaction conditions, such as the solvent and catalyst used, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent, and among these, it is more preferable to use propylene glycol monomethyl ether acetate.

[0061] Furthermore, it is preferable to use a catalyst in the reaction between an epoxy group and a carboxy group or a hydroxy group, and JP-A-9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0062] Next, the diol (d) represented by general formula (A-8) obtained by the reaction of the epoxy compound (a-1) with the (meth)acrylic acid derivative is reacted with a dicarboxylic acid or tricarboxylic acid or its acid anhydride (b), and a tetracarboxylic acid or its acid dianhydride (c), to obtain an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the following general formula (A-1).

[0063] [ka]

[0064] In formula (A-1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each R1 is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a (meth)acryloyl group or a substituent represented by the following general formula (A-2) or the following general formula (A-3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by the following general formula (A-4), and at least one Z is a substituent represented by the following general formula (A-4). n is a number with an average value of 1 to 20.

[0065] [ka]

[0066] [ka]

[0067] In formulas (A-2) and (A-3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site.

[0068] [ka]

[0069] In formula (A-4), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0070] The acid component used to synthesize the unsaturated group-containing alkali-soluble resin represented by general formula (A-1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by general formula (A-8). It is necessary to use a dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) in combination with a tetracarboxylic acid or its dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated or unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, or carbonyl groups.

[0071] Examples of the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their monoanhydrides.

[0072] Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0073] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0074] Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and the like, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0075] Among the above dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid are preferred, and 1,2,3,6-tetrahydrophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid are more preferred.

[0076] Examples of the acid monoanhydrides of the chain hydrocarbon dicarboxylic 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, diglycolic acid, and the like, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0077] Examples of the acid monoanhydrides of the alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0078] Examples of the acid monoanhydrides of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and the like, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0079] Among the above-mentioned dicarboxylic acid or tricarboxylic acid monoanhydrides, the acid monoanhydrides of succinic acid, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid are preferred, and the acid monoanhydrides of 1,2,3,6-tetrahydrophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid are more preferred.

[0080] In addition, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The acid monoanhydrides of the dicarboxylic acids or tricarboxylic acids described above may be used alone or in combination of two or more thereof.

[0081] Examples of the tetracarboxylic acid or its dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and dianhydrides thereof.

[0082] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0083] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0084] Examples of aromatic hydrocarbon tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-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.

[0085] Alternatively, bis(trimellitic anhydride) aryl esters can be used. Bis(trimellitic anhydride) aryl esters are a group of compounds produced, for example, by the method described in International Publication No. 2010 / 074065, and are structurally dianhydrides formed by ester bonding between two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, or terphenyldiol) and the carboxyl groups of two molecules of trimellitic anhydride. These compounds are hereinafter referred to as bis(trimellitic anhydride) esters of aromatic diols.

[0086] Among the above-mentioned tetracarboxylic acids or acid dianhydrides thereof, 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylethertetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are preferred, and 3,3',4,4'-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid are more preferred. Furthermore, among the above-mentioned tetracarboxylic acids or acid dianhydrides thereof, it is preferred to use the acid dianhydrides themselves. Furthermore, bis(trimellitic anhydrides) of naphthalenediol can also be preferably used. The above-mentioned tetracarboxylic acids or acid dianhydrides thereof, and bis(trimellitic anhydrides) of aromatic diols may be used alone or in combination of two or more.

[0087] The reaction of the diol (d) represented by the general formula (A-8) with the acid components (b) and (c) is not particularly limited, and known methods can be used. For example, JP-A-9-325494 describes a method in which an epoxy (meth)acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0088] Here, it is preferable to react the compound so that the terminals of the compound become carboxy groups, and the molar ratio of the epoxy (meth)acrylate (d), dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides (b), and tetracarboxylic acid dianhydride (c) is (d):(b):(c)=1.0:0.01-1.0:0.2-1.0.

[0089] For example, when using an acid monoanhydride (b) and an acid dianhydride (c), the molar ratio of the amount of acid component (b) to the amount of diol (d) containing a polymerizable unsaturated group, [(b) / 2 + (c)] / (d)], is preferably 0.5 to 1.0. A molar ratio of more than 0.5 prevents an increase in the amount of unreacted diol containing a polymerizable unsaturated group, thereby improving the stability of the alkali-soluble resin composition over time. On the other hand, a molar ratio of 1.0 or less prevents the end of the alkali-soluble resin represented by general formula (A-1) from becoming an acid anhydride, thereby preventing an increase in the amount of unreacted dianhydride, thereby improving the stability of the alkali-soluble resin composition over time. The molar ratios of components (b), (c), and (d) can be varied within the above-mentioned ranges to adjust the acid value and molecular weight of the alkali-soluble resin represented by general formula (A-1).

[0090] In the photosensitive resin composition of this embodiment, the content of component (A) is preferably 10% by mass to 80% by mass, and more preferably 10% by mass to 60% by mass, based on the total mass of the solids. When the content of component (A) is within the above range based on the total mass of the solids, alkali solubility is appropriately exhibited, resulting in good developability.

[0091] The acid value of component (A) is preferably 20 mgKOH / g to 200 mgKOH / g, and more preferably 30 mgKOH / g to 150 mgKOH / g. When the acid value is 20 mgKOH / g or more, the alkali solubility of the unexposed areas tends to be increased, and developability tends to be improved. When the acid value is 200 mgKOH / g or less, the alkali solubility of the exposed areas tends to be reduced, and developability tends to be improved. The acid value is measured by titration with a 1 / 10N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0092] Furthermore, the weight-average molecular weight (Mw) of component (A) measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) in terms of polystyrene is preferably 1,000 to 100,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. When the weight-average molecular weight (Mw) is 1,000 or more, the adhesion and flexibility of the cured film are enhanced, and the crosslinking density is easily adjusted, which facilitates improved developability. When the weight-average molecular weight (Mw) is 100,000 or less, the solubility of component (A) in solvents is enhanced, and compatibility with other components in the photosensitive resin composition is also enhanced, which suppresses aggregation of other components, thereby more easily suppressing light scattering on the surface and inside of the light-shielding film. As a result, patterning properties are improved, and developability is likely to be improved.

[0093] 1-2. (B) Photopolymerizable compound having at least two unsaturated bonds The component (B) forms an appropriate crosslinked structure when the photosensitive resin composition is cured, which facilitates improving the developability of the light-shielding film. Note that the component (B) does not have an acidic group that would impart alkali solubility.

[0094] Specific examples of 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, pentaerythritol tetra(meth)acrylate, dipe Examples of the ethylenic double bond-containing compound include (meth)acrylic acid esters such as 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 compounds having an ethylenic double bond such as dendritic polymers having a (meth)acrylic group.

[0095] Examples of the dendritic polymer include dendrimer acrylates, which are spherical macromolecules formed by radially assembling branch molecules having acrylic groups, hyperbranched acrylic polymers, hyperbranched acrylic oligomers, and dendritic polymers obtained by adding a polyvalent mercapto compound to part of the carbon-carbon double bonds in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specific examples include dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (B-1) with a polyvalent mercapto compound represented by the following general formula (B-2). From the viewpoint of facilitating the photopolymerization reaction, it is also preferable to use such polyfunctional dendritic polymers.

[0096] [ka]

[0097] In formula (B-1), R6 is a hydrogen atom or a methyl group, and R7 is R8(OH) k The remaining portion is obtained by donating r hydroxy groups out of k hydroxy groups to the ester bond in the formula. Preferred R8(OH) k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking multiple molecules of the polyhydric alcohol via ether bonds resulting from dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. k and r independently represent integers of 2 to 20, provided that k≧r.

[0098] [ka]

[0099] In formula (B-2), R9 is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, and s is 2 when R9 is a single bond, and is the same as the valence of R9 when R9 is a divalent to hexavalent group.

[0100] Examples of the polyfunctional (meth)acrylate represented by general formula (B-1) 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.

[0101] Examples of the polyvalent mercapto compound represented by general formula (B-2) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), and the like.

[0102] The component (B) may be one of these photopolymerizable compounds, or two or more of them may be used in combination. The component (B) can serve to crosslink the molecules of the component (A), and to perform this function, it preferably has three or more unsaturated bonds. Increasing the number of unsaturated bonds tends to increase the degree of curing of the light-shielding film and improve resolution.

[0103] Similarly, from the viewpoint of facilitating an increase in the degree of cure, the component (B) preferably has an acrylic equivalent, calculated by dividing the molecular weight by the number of (meth)acrylic groups in one molecule, of 50 g / eq to 300 g / eq, and more preferably 80 g / eq to 200 g / eq.

[0104] The mass ratio, where the total mass of component (A) is the numerator and the total mass of component (B) is the denominator, is preferably 30 / 70 to 90 / 10, and more preferably 50 / 50 to 70 / 30. When the blending ratio of component (A) is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to decrease in the unexposed areas, thereby preventing a decrease in solubility in alkaline developers. This reduces the likelihood of problems such as jagged or lacking sharpness in pattern edges. Furthermore, when the blending ratio of 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, because the acid value of the resin component is not too high, the solubility in alkaline developers in the exposed areas is less likely to increase, preventing the formed pattern from being thinner than the target line width or pattern defects.

[0105] 1-3.(C) Photopolymerization initiator There are no particular limitations on the component (C), so long as it is a compound that can initiate polymerization of an addition-polymerizable compound having a polymerizable unsaturated bond upon stimulation with light.

[0106] Examples of component (C) include acetophenone-based photopolymerization initiators, triazine-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, imidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, etc. In this specification, the term "photopolymerization initiator" is used to include sensitizers.

[0107] The component (D) preferably contains an oxime ester photopolymerization initiator. Oxime ester photopolymerization initiators have high sensitivity and can therefore easily improve developability.

[0108] Examples of the acetophenone-based photopolymerization initiator 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. Examples of commercially available products include Omnirad 127, Omnirad 369, Omnirad 1173, Omnirad 184, and Omnirad 651 (the Omnirad series is manufactured by IGM Resins BV).

[0109] Examples of triazine-based photopolymerization initiators 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, and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0110] Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-tert-butyl ether.

[0111] Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(N,N-diethylamino)benzophenone.

[0112] Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0113] Examples of the imidazole-based photopolymerization initiator 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.

[0114] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Examples of commercially available products include Omnirad TPO H and Omnirad 819 (the Omnirad series is manufactured by IGM Resins BV).

[0115] Examples of oxime ester photopolymerization initiators 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)- 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-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]-thiophenylmethane-1- 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]-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-bicycloheptanecarboxylate 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethan-1-one oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)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)-acetyloxime, 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, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanol Non-, 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.

[0116] Commercially available oxime ester photopolymerization initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (IRGACURE OXE-03, BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (IRGACURE OXE-04, BASF, and Lunar 6, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (TR -PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-831E (ADEKA Corporation), Omnirad 1312 (IGM Resins BV), and DFI-020 (Daito Chemix Co., Ltd.).

[0117] Examples of the oxime ester photopolymerization initiator include oxime ester compound photopolymerization initiators represented by general formula (C-1) or general formula (C-2).

[0118] [ka]

[0119] In formula (C-1), R 10 , R 11 are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 12 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Furthermore, the alkyl group may be a straight-chain, branched, or cyclic alkyl group.

[0120] [ka]

[0121] In formula (C-2), R 13 and R 14 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. 15 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. 13 ~R 15 Some of the hydrogen atoms in the group may be substituted with halogen atoms.

[0122] The content of component (C) is preferably 3.0% to 30.0% and more preferably 5.0% to 20.0% based on the total mass of components (A) and (B). When the content of component (C) is 3.0% or more, the sensitivity of the photosensitive resin composition is improved, and the photopolymerization rate can be sufficiently increased. When the content of component (C) is 30.0% or less, the sensitivity of the photosensitive resin composition is kept within an appropriate range, making it easy to obtain a cured film having the desired pattern line width and desired pattern edge shape.

[0123] 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 such 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.

[0124] 1-4. (D) At least one light-shielding component selected from the group consisting of black pigments and mixed color pigments The component (D) is a component that increases the light-shielding properties of the light-shielding film (decreases the light transmittance of the light-shielding film).

[0125] Component (D) is at least one light-shielding component selected from the group consisting of black pigments and mixed-color pigments. Any known light-shielding component selected from the group consisting of black pigments and mixed-color pigments can be used as component (D) without any particular restrictions. Component (D) is preferably dispersed so that the average particle size (average particle size measured with a laser diffraction / scattering particle size distribution analyzer or a dynamic light scattering particle size distribution analyzer) is 1 nm to 1,000 nm.

[0126] Examples of the black pigment include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, zirconium nitride, and the like.

[0127] Examples of the mixed-color pigment include mixed-color organic pigments in which at least two colors of 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 are mixed; and mixed-color inorganic pigments in which a white pigment such as titanium oxide or zinc oxide is mixed with the above-mentioned black pigment.

[0128] 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.

[0129] Examples of organic pigments that can be used as component (D) include, but are not limited to, those with the following Color Index numbers: 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.

[0130] The carbon black used in this specification may be surface-treated with a dye or the like to coat the surface, as described below. Dye-coated carbon black enhances the developability of the photosensitive resin composition and also facilitates improving the adhesion to the substrate, fine line reproducibility, and light-shielding properties of the resin film obtained by curing the composition, thereby facilitating increasing the resistance value of the resin film.

[0131] The dye may be any dye capable of adsorbing to the surface of carbon black, and may be a basic dye, acid dye, direct dye, reactive dye, or the like. When acidic functional groups are added to the surface of carbon black (oxidation treatment is performed) to enhance dispersibility, acid dyes (especially acid dyes having sulfonic acid groups or carboxy groups) that readily interact with the acidic functional groups are preferred. Furthermore, acid dyes or nonionic dyes are preferred over dyes having amino groups, etc., in order to suppress reaction with the acidic groups of component (A). Furthermore, dark-colored dyes are preferred in order to more easily improve the light-blocking properties of the resin film.

[0132] Specific examples of the dyes include food coloring dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, and Food Yellow No. 7; acid dyes of various colors such as Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz); Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, NY), and BASF Basacid Black SE 0228 (manufactured by BASF); Pontamine Brilliant Bond Blue A and other Pontamine Brilliant dyes. Bond Blue A and other Pontamine® dyes (Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.); Yellow Shade 16948 (Tricon), Direct Brilliant Pink B (Crompton & Knowles), Carta Black 2GT (Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz), Pergasol Yellow CGP (Ciba-Geigy), Pyrazol Black BG (JCI), Diazol Black RN Quad (JCJ), Pontamine Brilliant Bond Blue; Berncolor AYDirect dyes of various colors such as Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc., Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar dyes available from Levafix® dyes Dystar LP (Charlotte, NC), reactive dyes of various colors such as Procion Red H8B (Reactive Red 31) (JCI America), Neozapon Red 492 (BASF), Orasol Red G (Ciba-Geigy), Aizen Spilon Red C-BH (Hodogaya Chemical Company), Spirit Fast Yellow 3G, and Aizen Spilon Yellow Examples of suitable dyes include oil-soluble dyes such as C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), Morfast Black Concentrate A (manufactured by Morton-Thiokol), and CI Direct BLACK 38. These may be used alone or in combination of two or more.

[0133] The content of the dye is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 7% by mass, based on the total mass of the carbon black. The greater the amount of dye, the higher the resistance value of the resin film. By ensuring that the amount of dye is not excessive, it is possible to prevent thickening of the photosensitive resin composition due to excess dye and aggregation due to the excess dye inhibiting the dispersibility of other components.

[0134] The dye may also be laked with a metal or metal salt. By lakedizing the dye, the dye can be fixed to the surface of the carbon black via the metal or metal salt, thereby preventing the dye from detaching from the carbon black surface and reducing the aforementioned effects. Examples of the metal include aluminum, magnesium, calcium, strontium, barium, and manganese. Examples of the metal salt include the hydrochlorides and sulfates of these metals. The molar amount of the metal or metal salt is preferably 0.3 times or more, more preferably 0.5 times or more, and even more preferably 0.6 times or more, relative to the amount of the dye.

[0135] The amount of component (D) to be added can be determined arbitrarily depending on the desired degree of light blocking.

[0136] For example, when used as a black matrix, the content by mass of component (D) is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass, based on the total mass of the solid content in the photosensitive resin composition. When the blending amount of the light-shielding component is 20% by mass or more based on the solid content in the photosensitive resin composition, the light-shielding properties of the light-shielding film can be sufficiently enhanced. When the blending amount of the light-shielding component is 80% by mass or less based on the solid content in the photosensitive resin composition, the content of component (A), which originally serves as a binder, can be sufficiently increased, making it easier to improve the desired development characteristics and film-forming ability.

[0137] Furthermore, for example, when used as an overcoat layer, the content of component (D) is preferably 0.5% by mass to 10.0% by mass relative to the total mass of the solid content of the photosensitive resin composition. When the content is 0.5% by mass or more, even when external light incident on an organic EL panel is reflected by the organic EL panel, the reflected light is easily blocked, which tends to improve the visibility of the organic EL display device. When the content is 10.0% by mass or less, the light emitted by the organic EL panel is easily transmitted, which tends to reduce the amount of emitted light, which tends to reduce the power consumption of the organic EL display device. From the same viewpoint, the total mass of component (D) is more preferably 0.7% by mass to 4.5% by mass, and even more preferably 1.2% by mass to 3.5% by mass relative to the total mass of the solid content.

[0138] The component (D) is usually dispersed in a solvent to form a light-shielding component dispersion, which is then mixed with other formulation components, and a dispersant may be added at this time. The dispersant may be any known compound used to disperse 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.

[0139] Examples of dispersants for the light-shielding components 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 the dispersant for the light-shielding components is preferably 1% to 35% by mass, more preferably 2% to 25% by mass, based on the total mass of the light-shielding components. While high-viscosity substances such as resins generally have the effect of stabilizing dispersion, those without the ability to promote dispersion are not considered dispersants. However, this does not limit their use for the purpose of stabilizing dispersion.

[0140] 1-5. (E) Inorganic fine particles with a refractive index of 1.10 to 1.80 The component (E) makes it easier to lower the refractive index of the light-shielding film formed from the photosensitive resin composition.

[0141] Specific examples of inorganic fine particles that can be used include aluminum oxide, silicon oxide (silica), barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, sodium metasilicate, magnesium fluoride, and sodium hexafluoroaluminate (cryolite). Examples of silica include fumed silica, colloidal silica, and organosilica sol. Among these, silica is particularly preferred as the inorganic fine particle from the viewpoint of facilitating a reduction in reflectance.

[0142] The type of inorganic fine particles is not particularly limited, and they may be solid particles or hollow particles. Note that "hollow particles" refer to particles with a cavity inside. Furthermore, the method for producing component (E) (gas phase reaction, liquid phase reaction) and the shape (spherical, non-spherical) are not particularly limited. Furthermore, metal oxide particles whose surfaces have been treated with a coupling agent or the like may also be used.

[0143] The refractive index of the inorganic fine particles is preferably 1.20 to 1.60, more preferably 1.30 to 1.50. It is preferable to use inorganic fine particles with a refractive index somewhere between that of the light-shielding component and that of the transparent substrate or air adjacent to the light-shielding film. It is believed that the use of such particles reduces the difference in refractive index between the transparent substrate or air and the light-shielding film, thereby reducing reflectance. The refractive index of the inorganic fine particles is a value measured using an Abbe refractometer, and the refractive index value in this application refers to the refractive index value for light with a wavelength of 550 nm. The method for measuring the refractive index of component (E) using an Abbe refractometer is as follows: A powder of component (E) is mixed with a standard refractive index liquid having a known refractive index to obtain a transparent mixed liquid, and the refractive index of the component (E) is measured. The refractive index of the component (E) is calculated based on the change in refractive index between the standard refractive index liquid before and after mixing of component (E) and the amount of component (E) added to the standard refractive index liquid.

[0144] The refractive index of silica particles is 1.10 to 1.47. For example, ordinary silica particles (refractive index 1.45 to 1.47) can be used, or hollow silica particles with a low refractive index can be used to make the refractive index of the light-shielding film lower than that of a light-shielding film containing only ordinary silica particles. The refractive index of magnesium fluoride particles is 1.38 to 1.43. The refractive index of sodium hexafluoroaluminate is approximately 1.34.

[0145] The average primary particle diameter of the inorganic fine particles is preferably 1 nm to 100 nm, more preferably 10 nm to 80 nm. When the average primary particle diameter is 1 nm or more, particle aggregation is less likely to occur, and the dispersion stability of the inorganic fine particles is likely to be improved. This facilitates the segregation of the inorganic fine particles within the light-shielding film due to the component (F) described below, which facilitates segregation of a sufficient amount of inorganic fine particles, thereby further reducing the reflectance. Furthermore, by setting the average primary particle diameter of the inorganic fine particles to 100 nm or less, the segregation of the inorganic fine particles within the light-shielding film due to the component (F) described below is facilitated, which facilitates the inorganic fine particles to be unevenly distributed toward the film surface, further reducing the reflectance. Furthermore, it is also possible to prevent the inorganic fine particles unevenly distributed toward the film surface from reducing surface smoothness and the linearity of the cured film from being reduced due to scattering of exposure light. For the same reasons, when the inorganic fine particles are silica, the average primary particle diameter is preferably 1 nm to 100 nm, more preferably 10 nm to 80 nm.

[0146] The average primary particle diameter of inorganic microparticles is a value calculated by averaging the values ​​measured using a transmission electron microscope "JEM-2100Plus" (manufactured by JEOL Ltd.) with n = 3, on a measurement sample prepared by diluting a liquid containing inorganic microparticles with a solvent to a particle concentration of about 0.1 wt%, and dropping the resulting dispersion onto a metal mesh with a carbon support film.

[0147] The shape of the inorganic fine particles may be spherical or elliptical, but spherical is preferred because it is easier to reduce the refractive index and increase the strength of the light-shielding film. For example, the inorganic fine particles preferably have a sphericity of 1.0 to 1.5. If the sphericity of the inorganic fine particles is within this range, the particle shape will be close to a sphere. This allows the inorganic fine particles to be uniformly packed into a thin light-shielding film, allowing the formation of a light-shielding film in which the inorganic fine particles are not exposed to the outside from the film surface while maintaining the film surface smoothness. This makes it possible to obtain a light-shielding film with a low refractive index and sufficient strength.

[0148] The sphericity of the inorganic fine particles can be determined from the ratio of the longest diameter to the shortest diameter (average value of 100 arbitrary inorganic fine particles). Here, the longest diameter and the shortest diameter of the inorganic fine particles are values ​​determined by photographing the inorganic fine particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the inorganic fine particles from the obtained micrograph.

[0149] The method for producing inorganic fine particles is not particularly limited, and those produced by known methods such as a gas phase reaction method or a liquid phase reaction method can be used.

[0150] Component (E) may contain other ingredients as a dispersion of inorganic fine particles dispersed in a solvent. In this case, a dispersant may be added as another ingredient to promote the dispersion of the inorganic fine particles or stabilize the dispersibility. The dispersant may be any known compound (e.g., a compound commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) used in dispersing pigments (light-blocking components) without any particular restrictions. Furthermore, a dispersing resin other than the dispersant may be used in combination as long as it does not impair dispersion stability.

[0151] The dispersant that can be contained in component (E) is described below.

[0152] The dispersant has an acid value and an amine value, and both of the acid value and the amine value are preferably 10 mgKOH / g to 80 mgKOH / g. Preferably, one of the acid value and the amine value is 10 mgKOH / g to 80 mgKOH / g and the other is 30 mgKOH / g to 80 mgKOH / g. More preferably, both are 30 mgKOH / g to 80 mgKOH / g. An amine value of 10 mgKOH / g or more can improve the dispersibility of inorganic fine particles. On the other hand, a dispersant having only an amine value improves the dispersibility of inorganic fine particles, but reduces the solubility of the inorganic fine particles in the developer, which tends to leave residue at the pattern edge and reduce linearity. In contrast, a dispersant having an amine value of 10 mgKOH / g or more and an acid value of 10 mgKOH / g or more can improve the dispersibility of inorganic fine particles while facilitating high-resolution pattern formation. On the other hand, by setting both the acid value and the amine value to 80 mgKOH / g or less, the solubility of the inorganic fine particles protected by the dispersant in the developer is not excessively increased, making it easier to suppress a decrease in the definition of the formed pattern.

[0153] The acid value of a dispersant refers to the number of milligrams of KOH required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with JIS K 0070: 1992. The amine value of a dispersant refers to the number of milligrams of KOH equivalent to the amount of acid (acetic acid, etc.) required to neutralize 1 g of the resin component (solid content), and can be measured in accordance with JIS K 7237: 1995.

[0154] Examples of dispersants include alkylammonium salts and alkylolammonium salts of acidic polymers, alkylammonium salts and alkylolammonium salts of polymeric copolymers having acid groups, neutralized salts of polymers having alkylamino groups, and phosphate salts of polymeric copolymers. Among these, polymeric compounds having an alkylammonium salt structure are preferred, and alkylammonium salts of acidic polymers and alkylammonium salts of polymeric copolymers having acid groups are more preferred. By using a polymeric compound having an alkylammonium salt structure as a dispersant, the generation of agglomerated foreign matter of inorganic fine particles can be more significantly suppressed.

[0155] Examples of commercially available dispersants include DISPERBYK-140, 142, 145, 2001, 2025, and 9076 (all manufactured by BYK Japan, and "DISPERBYK" is a registered trademark of the company). Of the above commercially available products, DISPERBYK-140, 142, and 9076 are preferred, and DISPERBYK-140 and 9076 are more preferred.

[0156] The content by mass of the dispersant is preferably 2% to 60%, more preferably 3% to 40%, of the content by mass of the inorganic fine particles. Within this range, the dispersibility of the inorganic fine particles is likely to be improved, and the inorganic fine particles are likely to segregate in the light-shielding film due to the component (F) described below, and a sufficient amount of the inorganic fine particles is likely to segregate, which further reduces the reflectance.

[0157] The content of component (E) is preferably 1% by mass to 30% by mass, and more preferably 2% by mass to 10% by mass, based on the total mass of the solid content of the photosensitive resin composition. If the content of component (E) is 1% by mass or more, the reflectance is more likely to decrease. If the content is 30% by mass or less, components (A) and (B) are sufficiently contained, which makes it easier to improve developability.

[0158] 1-6.(F) Solvent The component (F) dissolves or disperses each component contained in the photosensitive resin composition, adjusts the viscosity of the photosensitive resin composition, and makes it easier to achieve both low reflectance and good developability.

[0159] The component (F) is a first solvent which is propylene glycol monomethyl ether acetate, and a ΔE ST and a second solvent (excluding propylene glycol monomethyl ether acetate) having a refractive index of 0.45 eV or more, and the content by mass of the second solvent is 4.0% to 60.0% based on the total mass of the solvent (F).

[0160] In this specification, ΔE ST The value of is calculated using a quantum chemistry calculation program. First, the structure of the compound is optimized. At this time, calculations can be performed using the density functional method at the B3LYP level, with 6-31G(d) as the basis function. For the obtained molecular structure, excited state calculations are performed using time-dependent density functional theory (Time-Dependent DFT) to determine the energy values ​​of the lowest excited singlet state S1 and the optimal excited triplet state T1 (E(S1) and E(T1) respectively), and ΔE ST =|E(S1)-E(T1)|. Gaussian 16, manufactured by Gaussian, USA, can be used as a quantum chemistry calculation program. Generally, as the overlap of the energy levels of the HOMO and LUMO increases, ΔE ST In addition, the HOMO and LUMO tend to overlap more in the vicinity of the polar functional group, and the ΔE of a solvent whose molecular structure is not rotationally symmetric, has polar functional groups, and has a large electron imbalance as a whole molecule is ST The value tends to be large.

[0161] The first solvent and ΔE ST The reason why low reflectance and good developability are achieved simultaneously by including a second solvent having a refractive index of 0.45 eV or more and the total mass of the second solvent being 4.0% to 60.0% with respect to the total mass of solvent (F) is not necessarily clear, but is thought to be as follows.

[0162] As described above, the second solvent, which has a non-rotationally symmetric molecular structure, polar functional groups, and a large electron imbalance in the molecule as a whole, is prone to polar interactions due to the large electron imbalance in the molecule as a whole, and therefore, sufficient polar interactions can be formed between the polar functional groups of the solvent and the inorganic fine particles, so that the inorganic fine particles are attracted to the film surface and easily segregated when the solvent evaporates.

[0163] Furthermore, the second solvent is likely to form polar interactions between its molecules and with other components in the photosensitive resin composition, thereby suppressing solvent evaporation during solvent drying. Therefore, by including 4.0% or more of the second solvent relative to the total mass of the (F) solvent, the solvent is likely to remain on the surface side of the coating film during drying, suppressing migration of the (E) component to the bottom side (substrate side) of the coating film and facilitating segregation of the (E) component to the film surface side. As a result, the cured film formed by subsequent curing contains a sufficient amount of the (E) component on the film surface side, which is thought to adjust the refractive index of the film surface side and reduce the reflectance of the film surface side. Furthermore, by limiting the content of the second solvent to 60% by mass or less, interactions between the molecules of the second solvent are likely to be suppressed, facilitating polar interactions between the polar functional groups of the solvent and the inorganic fine particles, resulting in a decrease in reflectance.

[0164] On the other hand, to obtain good developability, the alkali solubility of the coating film formed from the photosensitive resin composition must be sufficiently reduced by exposure. Therefore, to facilitate increasing the photoreactivity upon exposure, it is preferable, for example, that the amount of residual solvent in the coating film is sufficiently reduced at the time of exposure. However, when reducing the residual solvent in the coating film, the drying temperature may be set low or the drying time may be set short to facilitate maintaining the alkali solubility of the unexposed areas (to facilitate suppressing the reaction of unsaturated groups, etc., in components (A) and (B)). However, the second solvent has a large electron imbalance throughout the molecule, which is likely to cause polar interactions between the second solvent molecules and with other components in the photosensitive resin composition, which tends to suppress solvent volatilization during reduced-pressure drying and increase the amount of residual solvent in the coating film upon exposure. Therefore, by setting the mass content of the second solvent to 60.0% or less of the total mass of solvent (F), the solvent of the photosensitive resin composition is less likely to remain in the coating film upon exposure, which tends to improve the developability of the coating film.

[0165] ΔE ST As described above, solvents with a molecular structure of 0.45 eV or more are solvents that are not rotationally symmetric, have polar functional groups, and have a large electron imbalance in the molecule as a whole.

[0166] Examples of the second solvent include cyclohexanone, ethyl 3-ethoxypropionate (EEP), γ-butyrolactone, ethyl lactate (EL), ethylene glycol mono-normal butyl ether, diethylene glycol methyl ethyl ether (EDM), a compound represented by general formula (F-1), or a compound represented by general formula (F-2).

[0167] Among these, from the viewpoint of facilitating a reduction in reflectance, the second solvent preferably contains ethyl 3-ethoxypropionate (EEP), a compound represented by general formula (F-1), or a compound represented by general formula (F-2), more preferably contains a compound represented by general formula (F-1) or a compound represented by general formula (F-2), and further preferably contains a compound represented by general formula (F-2), and among the compounds represented by general formula (F-2), Ra It is most preferable that the compound represented by general formula (F-2) contains a solvent in which the alkyl group is a methyl group or an n-butyl group. The compound represented by general formula (F-2) has a relatively low polarity alkyl group and a highly polar amide group at both ends, which increases the electron imbalance of the molecule as a whole, and therefore ΔE ST Therefore, the polar functional groups of the solvent and the inorganic fine particles tend to interact with each other, and when the solvent evaporates, the inorganic fine particles tend to be attracted to the film surface and segregate, which tends to lower the reflectance.

[0168] [ka]

[0169] In formula (F-1), R a , R c and R d each independently represents an alkyl group having 1 to 4 carbon atoms, and R b represents an alkylene group having 1 to 4 carbon atoms.

[0170] [ka]

[0171] In formula (F-2), R a represents an alkyl group having 1 to 4 carbon atoms.

[0172] The second solvent has a ΔE ST Preferably, the second solvent contains a solvent having a higher ΔE ST By including a solvent with a value of ΔE, the interaction between the solvent and the inorganic particles becomes greater, which makes it easier for the reflectance to decrease. ST When two or more solvents having a VI of 0.45 eV or more are contained, the solvent with the highest content may satisfy the above-mentioned preferable range.

[0173] The second solvent preferably contains a solvent having a boiling point of 100°C to 260°C, more preferably a solvent having a boiling point of 120°C to 260°C, even more preferably a solvent having a boiling point of 150°C to 260°C, and most preferably a solvent having a boiling point of 210°C to 260°C. By including a solvent having a boiling point of 100°C or higher, bumping is less likely to occur, making it easier to obtain a coating film with good surface condition. Furthermore, by including a solvent having a boiling point of 100°C or higher, the solvent drying speed can be appropriately adjusted, facilitating segregation of inorganic fine particles. Furthermore, by including a solvent having a boiling point of 150°C or higher, solvent evaporation during solvent drying is more likely to be suppressed, suppressing migration of component (E) to the bottom side (substrate side) of the coating film and making it easier for component (E) to segregate toward the film surface. Having a boiling point of 210°C or higher can further facilitate segregation of component (E) toward the film surface due to the same effect as above. Furthermore, by including a solvent having a boiling point of 260°C or less, drying under reduced pressure becomes easier, and the amount of solvent in the coating film during exposure can be easily reduced, which tends to improve the developability of the coating film.

[0174] Component (F) may contain a solvent other than the first and second solvents, such as decane.

[0175] The amount of the first solvent blended is preferably 45.0 to 96.0 mass%, more preferably 65.0 to 96.0 mass%, even more preferably 80.0 to 96.0 mass%, and most preferably 90.0 to 96.0 mass%, based on the total mass of component (F). By increasing the amount of the first solvent blended, it becomes easier to further improve the solubility of components (A) and (B) and the dispersibility of component (D).

[0176] The amount of the second solvent is preferably 4.0% to 55.0% by mass, more preferably 4.0% to 35.0% by mass, even more preferably 4.0% to 20.0% by mass, and most preferably 4.0% to 10.0% by mass, based on the total mass of component (F). By setting the amount of the second solvent to 55.0% by mass or less, the solvent drying rate can be appropriately adjusted, making it easier to improve the developability of the coating film. In particular, by setting the amount of the second solvent to 35.0% by mass or less, it is easier to improve the developability of the coating film, even when the coating film is dried under drying conditions that are favorable from the perspective of production takt time, as described in "4-1. Coating Film Formation Step" below (conditions in which the ultimate pressure reaches 50 to 1,000 Pa in 10 to 50 seconds: for example, conditions (drying conditions 1) in which the pressure is reduced to 50 Pa in 45 seconds, as described in the Examples).

[0177] The blending amount of the component (F) is preferably 40% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 80% by mass to 90% by mass, based on the total mass of the photosensitive resin composition.

[0178] 1-7.Other ingredients The photosensitive resin composition may contain other components, as needed, such as an epoxy compound and its curing agent and curing accelerator, a coupling agent, a surfactant, a resin other than the alkali-soluble resin, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, and an ultraviolet absorber.

[0179] Examples of the epoxy compound 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.), 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, glycidyl ethers of polyhydric alcohols, and glycidyl ethers of polycarboxylic acids. esters, 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(3,4-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.), multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 2,Examples of epoxy compounds include alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 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. Among these, epoxy compounds having the above-mentioned aromatic structure are preferred from the viewpoint of improving the flatness and low gas generation of the coating film or cured film.

[0180] Examples of the curing agent include amine compounds that contribute to the curing of epoxy resins, polycarboxylic acid compounds or anhydrides thereof, thermally decomposable esters of polycarboxylic acids, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. Among these, it is preferable to select from the group consisting of polycarboxylic acids or anhydrides thereof, and thermally decomposable esters of polycarboxylic acids.

[0181] Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undec-7, and 1,5-diazabicyclo[4.3.0]non-5-ene, phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphinetriphenylborane, and metal compounds such as tin octylate. Among these, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or a salt thereof is preferred.

[0182] Examples of coupling agents include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-ureidopropyltriethoxysilane, titanium-based coupling agents, and aluminum-based coupling agents, etc. Among these, 3-isocyanatepropyltriethoxysilane is preferred.

[0183] Examples of surfactants include compounds containing hydrocarbon chains in the side chains, silicone-containing compounds, and fluorine-based compounds.

[0184] Examples of compounds containing a hydrocarbon chain in the side chain include polymers obtained by polymerizing (meth)acrylic acid alkyl esters. Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid t-butyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid 2-ethylhexyl ester, and (meth)acrylic acid isononyl ester.

[0185] Examples of silicone-containing compounds include the reaction product of (meth)acrylic acid with a hydroxy group-containing silicone (e.g., α,ω-polydimethylsilicone diol) and the reaction product of (meth)acrylic acid with an epoxy group-containing silicone (e.g., polydimethylsilicone containing pendant epoxy groups).

[0186] Examples of the fluorine-based compound include perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkyl ammonium salt, oligomer containing a perfluoroalkyl group and a hydrophilic group, oligomer containing a perfluoroalkyl group and a lipophilic group, oligomer containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group, urethane containing a perfluoroalkyl and a hydrophilic group, perfluoroalkyl ester, perfluoroalkyl phosphate ester, fluorine-containing organic compounds such as compounds containing a fluorine atom in the side chain, and the like.

[0187] The surfactant may also contain a crosslinking group, preferably an epoxy group or an ethylenically unsaturated group.

[0188] Examples of commercially available surfactants include DOWSIL SH 3775 M Fluid (manufactured by Dow-Toray Industries, Inc.), MEGAFACE EFS-131, MEGAFACE EFS-321, MEGAFACE EFS-521, and MEGAFACE EFS-801 (manufactured by DIC Corporation).

[0189] Of these, the surfactant is preferably a silicone-containing compound.

[0190] The content of the surfactant is preferably 0.01% by mass to 10.00% by mass, more preferably 0.01% by mass to 5.00% by mass, and even more preferably 0.01% by mass to 1.00% by mass, based on the total solid content of the photosensitive resin composition. By setting the content of the surfactant to 0.01% by mass or more, smoothness tends to be improved, and by setting it to 10.00% by mass or less, the surfactant is less likely to aggregate, making it easier to improve smoothness.

[0191] Examples of resins other than alkali-soluble resins include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

[0192] Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

[0193] Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of the filler include glass fiber, etc.

[0194] Examples of the defoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic-based compounds.

[0195] Examples of the ultraviolet absorber include a benzotriazole compound, a benzophenone compound, a triazine compound, etc. The photosensitive resin composition may contain additives such as a resin other than component (A), such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent, as needed.

[0196] 2. Preparation of photosensitive resin composition The photosensitive resin composition can be prepared by mixing and dispersing the above components (A) to (F) and, optionally, other components. For example, the photosensitive resin composition can be obtained by mixing a light-shielding component dispersion containing components (A), (B), (C), and (D), an inorganic fine particle dispersion containing component (E), and component (F).

[0197] By incorporating a dispersant into the inorganic fine particles (E) in advance, it is possible to improve the dispersion stability of the inorganic fine particles and prevent the generation of agglomerated foreign matter when they are mixed with other resin components.

[0198] 3. Light-shielding film The light-shielding film according to this embodiment is formed by applying a photosensitive resin composition to a substrate or the like to form a coating film, and optionally, by carrying out a step of exposing the coating to light and / or heat treating the coating film.

[0199] The substrate to which the photosensitive resin composition is applied may be made of a known material, such as glass or a polyimide film.

[0200] The light-shielding film may be a patterned layer or a non-patterned layer. The method for producing a light-shielding film having a pattern is not limited to a photolithography method involving exposure and alkaline development, and the pattern may be formed by screen printing or the like.

[0201] For example, when the light-shielding film is used as a black matrix, a photosensitive resin composition is applied to a glass substrate, the pressure is reduced to 50 Pa in 45 seconds using a vacuum dryer at 23°C to evaporate the solvent, the substrate is pre-baked at 90°C for 1 minute using a hot plate, and the substrate is post-baked at 230°C for 30 minutes using a hot air dryer. The resulting 1.0 μm light-shielding film preferably has a reflectance of less than 9.0%, more preferably less than 7.0%, even more preferably less than 5.0%, and most preferably less than 4.0%. The reflectance is the reflectance value of the light-shielding film side measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) under conditions of illuminant C, an incident angle of 2°, and a wavelength range of 380 to 780 nm.

[0202] Furthermore, when the light-shielding film is used as an overcoat layer, a photosensitive resin composition is applied to a glass substrate so that the resin film has a thickness of 3.0 μm. The resin film is then heated at 85°C for 1 minute and then further heated at 85°C for 60 minutes. The resulting substrate with a 3.0 μm light-shielding film preferably has a transmittance of 30% to 80%, more preferably 40% to 70%. A transmittance of 30% or more facilitates blocking of reflected light even when external light incident on the organic EL panel is reflected by the organic EL panel, thereby improving the visibility of the organic EL display device. A transmittance of 80% or less facilitates transmission of light emitted by the organic EL panel, thereby reducing the amount of emitted light and thereby reducing the power consumption of the organic EL display device. The transmittance is the average value measured from the resin film side using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) under conditions of Illuminant C, an incident angle of 0°, and a wavelength range of 440 to 650 nm.

[0203] 4. Light-shielding film manufacturing method The method for producing a light-shielding film according to the present embodiment includes a coating film formation step of applying a photosensitive resin composition to a substrate to form a coating film, and optionally includes an exposure step and / or a heat treatment step. When the light-shielding film is patterned, a desired pattern shape can be formed by defining light-exposed and non-light-exposed areas in the exposure step using a photomask or the like, curing only the light-exposed areas, and dissolving the other areas with an alkaline solution.

[0204] 4-1. Paint film formation process The photosensitive resin composition can be applied to a substrate by known methods such as a solution immersion method, a spray method, a method using a roller coater, a land coater, a slit coater, a spinner, etc. After applying the composition to a desired thickness by these methods, the composition is dried, and then the solvent is further removed (pre-baked) to form a coating film.

[0205] Drying may be carried out by a method such as vacuum drying under conditions such that the ultimate pressure is 5 to 1000 Pa in 10 to 180 seconds. Alternatively, degassing may be carried out all at once until the desired ultimate pressure is reached, or the pressure may be reduced stepwise to prevent film defects such as bumping. From the viewpoint of production takt time, drying is preferably carried out under conditions such that the ultimate pressure is 50 to 1000 Pa in 10 to 50 seconds.

[0206] Pre-baking is carried out by heating in an oven, on a hot plate, or the like, vacuum drying, or a combination of these. The heating temperature and heating time in pre-baking can be appropriately selected depending on the solvent used, but it is preferable to carry out pre-baking at 80 to 120°C for 1 to 10 minutes, for example.

[0207] 4-2. Exposure process The exposure can be carried out by irradiating a part of the coating film with radiation through a photomask, which causes the part of the coating film corresponding to the pattern to be photocured.

[0208] 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.

[0209] The exposure device used for exposure and its exposure irradiation conditions can be selected appropriately. Examples of 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 radiation. Furthermore, the wavelength of the irradiated radiation is preferably 250 nm to 400 nm. The radiation exposure dose is 25 mJ / cm.2 ~3000mJ / cm 2 It is preferable that:

[0210] 4-3.Developing process After exposure, the irradiated coating film is developed with an alkali to remove the unexposed areas of the coating film.

[0211] Examples of the method for developing the coating film include shower development, spray development, dip (immersion) development, puddle (liquid puddle) development, etc. The development can be carried out using a commercially available developing machine, ultrasonic cleaner, etc.

[0212] 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.

[0213] 4-4. Heat treatment process The formed coating film may be subjected to a heat treatment, which promotes a thermal crosslinking reaction and tends to improve the adhesion between the light-shielding film and the substrate.

[0214] The heat treatment can be carried out by a known method (heating with an oven, a hot air blower, a hot plate, an infrared heater, or the like, vacuum drying, or a combination thereof).

[0215] The heat treatment conditions are not particularly limited as long as the temperature is such that the coating film is fully cured (post-baked).The heating temperature is preferably 60 to 250° C. for 20 to 60 minutes.

[0216] After heat curing, the cured film may be washed with short-wave radiation to remove organic contaminants from the surface of the coated film.

[0217] The cleaning can be carried out by irradiating ultraviolet rays with wavelengths of 184.9 nm and 253.7 nm using a low-pressure mercury lamp, for example, at a dose of 1000 mJ.

[0218] 5. Color filters The color filter according to this embodiment includes the light-shielding film. For example, the light-shielding film can be used as a black matrix, a black column spacer, a frame, or the like of the color filter.

[0219] The color filter can be formed by any known method, such as a method of applying a color resist material, exposing it to light, and developing it to form a pattern, a method of transferring a photosensitive transfer material, exposing it to light, and developing it to form a pattern, or an inkjet method.

[0220] For example, a color filter having the above-mentioned light-shielding film as a black matrix is ​​produced by forming a light-shielding film having a thickness of 1.0 to 2.0 μm on a transparent substrate, and then 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.

[0221] Furthermore, when the light-shielding film is to be used as a black column spacer, a single black resist may be used to form a plurality of portions with different film thicknesses, one of which may function as a spacer and the other as a black matrix.

[0222] 6. Touch panel The touch panel according to the present embodiment includes the light-shielding film, which can be used as a black matrix, a black column spacer, a frame, or the like of the touch panel.

[0223] The touch panel according to this embodiment may be a known touch panel. It may be any of a variety of touch panel types, including resistive, capacitive, surface acoustic wave, infrared, electromagnetic induction, image recognition, and optical sensor types. There are types that detect a touch by contact with the touch panel, and types that detect a touch by the proximity of a finger or pen to the touch panel, and either type may be used.

[0224] 7.Display device The display device according to this embodiment has the above-described light-shielding film.

[0225] The display device according to this embodiment may be a known display device, such as a liquid crystal display device or an organic electroluminescence display device.

[0226] The photosensitive resin composition according to this embodiment is particularly useful as a color filter ink used in liquid crystal display devices, and a light-shielding film formed therefrom is useful as a color filter black matrix, etc. In addition to being used as a color filter ink for color liquid crystal displays, the photosensitive resin composition of the present invention can also be used as an ink material for color separation or light-shielding in various multicolor display devices such as organic EL display devices typified by organic EL elements and color liquid crystal display devices, or as an overcoat (OC) layer with appropriate light-shielding properties that can block external light reflected by organic EL panels.

[0227] The light source of the display device may be a known light source such as an organic electroluminescence (EL) light source or a laser light-emitting diode (LED) light source. The display device may also have a configuration in which a wavelength conversion layer containing quantum dots or a phosphor compound is disposed between the light source and the cured film-coated substrate. The cured film-coated substrate has good flexibility resistance, particularly when it is formed into a thick film having a thickness of 2 μm or 3 μm or more. Therefore, it is useful as a light-shielding film disposed laterally of the LED light source in an LED display having such a thickness to prevent lateral light leakage.

[0228] In particular, since the light-shielding film can reduce reflectance, when used in applications where the film surface is arranged inside a display device such as a liquid crystal display, it can suppress loss of light from an internal light source due to reflection inside the device. Furthermore, when used in applications where the film surface is arranged outside a display device such as an organic LED (OLED), it can improve contrast in bright areas by reducing reflection of external light, and can improve light extraction efficiency from the light-emitting side to improve luminous efficiency.

[0229] 8.Other uses The photosensitive resin composition according to this embodiment is useful as a color filter ink used in imaging devices. The light-shielding film according to this embodiment is also useful as a black matrix for liquid crystal projection. The photosensitive resin composition according to this embodiment can also be used as an ink material for color separation or light blocking in various multicolor displays such as image sensors. Suitable sensors include light (laser) detection and ranging (LiDAR) sensors for autonomous driving vehicles and sensors used in components requiring precise light-receiving sensitivity, such as encoder light-receiving elements. [Example]

[0230] 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.

[0231] First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin, component (A), will be explained. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0232] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter (weight: W0(g)), weighed (W1(g)), and heated at 160°C for 2 hours, and the weight (W2(g)) was calculated from the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0233] [Acid value] The resin solution was dissolved in tetrahydrofuran and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-A19" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value per 1 g of the sample (synthetic resin solution).

[0234] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8320GPC" (manufactured by Tosoh Corporation, developing solvent: tetrahydrofuran, columns: PL1110-6540 (1 column) + PL1110-6530 (1 column) + PL1110-6525 (1 column) + PL1110-6520 (1 column), column temperature: 40°C, flow rate: 1.0 mL / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by SAS Corporation, polystyrene kit).

[0235] [Average primary particle size] The inorganic fine particle-containing solution was diluted with a solvent to a particle concentration of about 0.1 wt%, and the resulting dispersion was dropped onto a metal mesh with a carbon support film to create a measurement sample, which was then observed using a transmission electron microscope "JEM-2100Plus" (manufactured by JEOL Ltd.) to determine the particle size. The number of measurements was n=3 for each.

[0236] The abbreviations used in the synthesis examples are as follows: AA: acrylic acid BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. (An epoxy resin of general formula (A-5) where Ar is a benzene ring and l is 0.) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride PGMEA: Propylene glycol monomethyl ether acetate TEAB: Tetraethylammonium bromide

[0237] [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 react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged to the flask and stirred at 120-125°C for 6 hours to obtain polymerizable unsaturated group-containing alkali-soluble resin (A)-1. The solids concentration of the resulting resin solution was 56.1 mass%, the acid value (solids equivalent) was 103 mg KOH / g, and the Mw by GPC analysis was 3600.

[0238] [Preparation example D] 1000 g of carbon black (TPX-1099, manufactured by Cabot Corporation) was mixed with water to prepare 10 L of slurry, which was stirred at 95°C for 1 hour, allowed to cool, and then washed with water. This was mixed again with water to prepare 10 L of slurry, to which 42.9 g of 70% nitric acid was added and stirred at 40°C for 4 hours. This was allowed to cool, washed with water, and then mixed again with water to prepare 10 L of slurry. 769.2 g of 13% aqueous sodium hypochlorite solution was added and stirred at 40°C for 6 hours. This was allowed to cool, washed with water, and then mixed again with water to prepare 10 L of slurry. 38.1 g of a 38.4% pure dye (CI Direct BLACK 38) was added and stirred at 40°C for 1 hour. 10.1 g of aluminum sulfate was then added and stirred at 40°C for 1 hour. This was allowed to cool, washed with water, filtered, and dried to obtain dye-coated carbon black.

[0239] The dye-coated carbon black, polymer dispersant, and PGMEA were mixed and dispersed in a bead mill to obtain carbon black dispersion (D)-1 having a dye-coated carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 10.0% by mass.

[0240] Photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 10 were prepared in the amounts (unit: parts by mass) shown in Tables 2 and 3. The ingredients used in Tables 2 and 3 are as follows.

[0241] (Alkali-soluble resin containing unsaturated groups) (A)-1: Alkali-soluble resin obtained in Synthesis Example 1 above

[0242] (Photopolymerizable compound) (B)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent: 96 g / eq to 115 g / eq), manufactured by Nippon Kayaku Co., Ltd.)

[0243] (Photopolymerization initiator) (C)-1: ADEKA Arcles NCI-831E, manufactured by ADEKA Corporation, "ADEKA Arcles" is a registered trademark of the company.

[0244] (Carbon black dispersion) (D)-1: Dye-coated carbon black obtained in Preparation Example D. Pigment dispersion (solid content 35% by mass) in PGMEA solvent with a concentration of 25% by mass and a polymer dispersant concentration of 10% by mass.

[0245] (Inorganic fine particle dispersion) (E)-1: Silica dispersion (solid content 25% by mass) in PGMEA solvent containing 20% ​​by mass of silica particles with an average primary particle diameter of 76 nm and 5% by mass of polymer dispersant

[0246] (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (F)-2: 3-butoxy-N,N-dimethylpropanamide (F)-3: 3-Methoxy-N,N-dimethylpropanamide (F)-4: Ethyl 3-ethoxypropionate (EEP) (F)-5: γ-butyrolactone (F)-6: Cyclohexanone (ANON) (F)-7: Ethyl lactate (EL) (F)-8: Ethylene glycol mono-n-butyl ether (F)-9: Diethylene glycol methyl ethyl ether (EDM) (F)-10: Decan

[0247] (F) Boiling point and ΔE of -2 to 10 ST is shown in Table 1.

[0248] [Table 1]

[0249] (Other ingredients) (X)-1: DOWSIL SH3775M, manufactured by Dow Chemical Japan Co., Ltd. "DOWSIL" is a trademark of the company. (X)-2:3-Isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0250] [Table 2]

[0251] [Table 3]

[0252] [evaluation] The following evaluations were carried out using the light-shielding films formed from the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 10. The evaluation results are shown in Tables 4 and 5.

[0253] <Reflectance evaluation> Each composition obtained above was applied to a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.0 μm. The solvent was evaporated using a vacuum dryer at 23°C under reduced pressure to 50 Pa in 45 seconds, and then the film was pre-baked at 90°C for 1 minute using a hot plate to produce a light-shielding film. This was followed by thermal post-baking at 230°C for 30 minutes using a hot air dryer. A grade of fair or better was considered acceptable.

[0254] (Evaluation method) Using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), the reflectance of the light-shielding film side was measured under the conditions of light source C, an incident angle of 2°, and a wavelength range of 380 to 780 nm.

[0255] (Reflectivity evaluation criteria) ◎: Reflectance is less than 5.0% ○: Reflectance is 5.0% or more and less than 7.0% △: Reflectance is 7.0% or more and less than 9.0% ×: Reflectance is 9.0% or more

[0256] <Developability evaluation> Each composition obtained above was applied to a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.0 μm. The solvent was evaporated using a vacuum dryer at 23°C by reducing the pressure to 50 Pa for 45 seconds (drying condition 1) or to 5 Pa for 180 to 300 seconds (drying condition 2). The film was then pre-baked at 90°C for 1 minute using a hot plate to prepare a light-shielding film pre-baked by drying the solvent under drying condition 1 and a light-shielding film pre-baked by drying the solvent under drying condition 2. The film was then dried under an i-line irradiance of 30 mW / cm. 2 30mJ / cm with an ultra-high pressure mercury lamp 2 The film thickness was measured by the method described below (hereinafter, the film thickness measured here may also be referred to as "film thickness after photocuring").

[0257] Next, the exposed coated plate was placed in a 0.04% aqueous potassium hydroxide solution at 23°C and heated at 1 kgf / cm 2 After 40 seconds of development, the shower pressure was 5kgf / cm 2 After that, the film thickness was measured by the method described below (hereinafter, the film thickness measured here will also be referred to as "film thickness after post-baking"), and the remaining film ratio was calculated from the following formula (A) for the light-shielding film that had been dried under drying condition 1 and the light-shielding film that had been dried under drying condition 2. A grade of fair or better was considered to be acceptable. Formula (A) (Residual film ratio) = ((Film thickness after post-baking) / (Film thickness after photo-curing)) × 100

[0258] (Film thickness evaluation method) Using a step gauge ("Tencor P-17" manufactured by KLA-Tencor Corporation), the step between the glass substrate surface and the cured film surface was measured under conditions of a measurement range of 500 μm, a scanning speed of 50 μm / sec, and a sampling rate of 20 Hz, and the average value was taken as the average thickness of the cured film.

[0259] (Evaluation criteria for developability) 〇: The remaining film rate is 90% or more when the pressure is reduced to 50 Pa in 45 seconds (drying condition 1). In addition, the remaining film rate is 90% or more when the pressure is reduced to 5 Pa for 180 to 300 seconds (drying condition 2). △: The remaining film rate when the pressure is reduced to 50 Pa in 45 seconds (drying condition 1) is less than 90%. The remaining film rate is 90% or more when the pressure is reduced to 5 Pa for 180 to 300 seconds (drying condition 2). ×: The remaining film rate is less than 90% regardless of the reduced pressure drying conditions.

[0260] [Table 4]

[0261] [Table 5]

[0262] From the results of Examples 1 to 18 and Comparative Examples 1 to 10, it was found that a light-shielding film formed from a photosensitive resin composition containing a first solvent and a second solvent as (F), where the content by mass of the second solvent is 4.0% to 60.0% relative to the total mass of the solvent (F), can achieve both low reflectivity and good developability. In particular, it was found that Examples 1, 2, 6, 7, 14, and 15, which contain a solvent represented by general formula (F-2) as the second solvent, have lower reflectivity than the other Examples. [Industrial Applicability]

[0263] The photosensitive resin composition of the present invention can provide a photosensitive resin composition for black matrices that achieves both high light-shielding properties and low reflectance, and a light-shielding film, a color filter, and a touch panel using the same. Furthermore, the color filter and the touch panel can provide various display devices with excellent visibility.

Claims

1. (A) an unsaturated group-containing alkali-soluble resin; (B) a photopolymerizable compound having at least two unsaturated bonds; (C) a photopolymerization initiator; (D) at least one light-shielding component selected from the group consisting of black pigments and mixed color pigments; (E) inorganic fine particles having a refractive index of 1.10 to 1.80; (F) a solvent; Including, The solvent (F) is a first solvent which is propylene glycol monomethyl ether acetate, and a solvent having a ΔE ＳＴ a second solvent (excluding propylene glycol monomethyl ether acetate) having a valence energy of 0.45 eV or more, The content by mass of the second solvent is 4.0% to 60.0% based on the total mass of the solvent (F). Photosensitive resin composition.

2. The (E) inorganic fine particles are silica particles. The photosensitive resin composition according to claim 1 .

3. The (E) inorganic fine particles have an average primary particle diameter of 1 nm to 100 nm. The photosensitive resin composition according to claim 1 .

4. The second solvent contains a solvent represented by the following general formula (F-2): The photosensitive resin composition according to claim 1 . 【Chemical 1】 (In the general formula (F-2), R ａ represents an alkyl group having 1 to 4 carbon atoms.

5. A light-shielding film formed from the photosensitive resin composition according to any one of claims 1 to 4.

6. A color filter comprising the light-shielding film according to claim 5 .

7. A touch panel comprising the light-shielding film according to claim 5 .

8. A display device comprising the color filter according to claim 6.

9. A display device comprising the touch panel according to claim 7.

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