Method for producing carboxyl group-containing resin and method for controlling molecular weight of carboxyl group-containing resin

Abstract

Provided are a method for producing a carboxy-group-containing resin that permits control of the molecular weight and has excellent performance stability between production lots, and a method for controlling the molecular weight of a carboxy-group-containing resin. The method for producing a carboxy group-containing resin of the present invention has a step A that reacts an epoxy compound (a) and an unsaturated monobasic acid (b) in an organic solvent and obtains a first reaction product A-containing solution, a step B that controls the water content of the first reaction product A-containing solution to obtain a second reaction product A-containing solution, and a step C that adds a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing solution and reacts to obtain a carboxy-group-containing resin.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a carboxyl group-containing resin, a method for producing an ink, a method for producing a photosensitive resin composition, a method for producing a cured product, a method for producing a black matrix, a method for producing an image display device, and a method for controlling the molecular weight of a carboxyl group-containing resin. This application claims priority based on Japanese Patent Application No. 2020-182984, filed on October 30, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] A color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, followed by the formation of pixels of three or more different colors, such as red, green, and blue, in a grid, stripe, mosaic, or other pattern. The pattern size varies depending on the application of the color filter and the individual colors, but is usually around 5 to 700 μm.

[0003] Currently, photolithography using a photosensitive resin composition is known as a typical method for producing color filters. When producing a color filter by photolithography, a photosensitive resin composition containing an alkali-developable carboxyl group-containing resin is first applied to a transparent substrate, dried, and then imagewise exposed and developed using an alkali developer, followed by curing at a high temperature of 200°C or higher to form a pattern. However, such photosensitive resin compositions vary in line width and film thickness depending on the molecular weight of the carboxyl group-containing resin, and large differences in molecular weight between production lots of the carboxyl group-containing resin have led to problems such as a decrease in color filter yield.

[0004] In light of this, there is a need for a method for controlling the molecular weight of a carboxyl group-containing resin and for stably producing the same. For example, Patent Documents 1 and 2 describe methods for producing a carboxyl group-containing resin using specific conditions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2000-336116 [Patent Document 2] Japanese Patent Application Publication No. 2005-41958 Summary of the Invention [Problem to be solved by the invention]

[0006] When the present inventors produced carboxyl group-containing resins using the production methods described in Patent Documents 1 and 2, they found that the stability of molecular weight between production lots was insufficient.

[0007] Therefore, an object of the present invention is to provide a method for producing a carboxyl group-containing resin that allows control of the molecular weight and has excellent performance stability between production lots, and a method for controlling the molecular weight of a carboxyl group-containing resin. [Means for solving the problem]

[0008] As a result of extensive investigations aimed at solving the above problems, the present inventors have found that the above problems can be solved by producing a carboxyl group-containing resin using a specific method.

[0009] [1] Step A of reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a liquid containing a first reaction product A; A step B of controlling the water content of the first reaction product A-containing liquid to obtain a second reaction product A-containing liquid; and step C of adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid and reacting them to obtain a carboxy group-containing resin. [2] The method for producing a carboxyl group-containing resin according to [1], wherein water is added to the first reaction product A-containing liquid to control the water content of the first reaction product A-containing liquid, thereby obtaining the second reaction product A-containing liquid. [3] The method for producing a carboxyl group-containing resin according to [2], wherein water is added to the first reaction product A-containing liquid so that the moisture content of the second reaction product A-containing liquid is 0.1 mass % or more and 0.5 mass % or less. [4] The method for producing a carboxyl group-containing resin according to any one of [1] to [3], wherein in the step C, a polyhydric alcohol (e) is further added and reacted. [5] The method for producing a carboxyl group-containing resin according to [4], wherein the polyhydric alcohol (e) includes trimethylolpropane. [6] The method for producing a carboxy group-containing resin according to any one of [1] to [5], wherein the polybasic acid dianhydride (c) contains biphenyltetracarboxylic dianhydride. [7] The method for producing a carboxyl group-containing resin according to any one of [1] to [6], wherein the polybasic acid monoanhydride (d) includes tetrahydrophthalic anhydride. [8] A method for producing an ink containing (A) an alkali-soluble resin, an organic solvent, and (D) a colorant, comprising: A method for producing an ink, comprising blending a carboxyl group-containing resin produced by the production method according to any one of [1] to [7] as the alkali-soluble resin (A). [9] A method for producing a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, comprising: A method for producing a photosensitive resin composition, comprising blending, as the alkali-soluble resin (A), a carboxyl group-containing resin produced by the production method according to any one of [1] to [7].

[10] The method for producing a photosensitive resin composition according to [9], wherein the photosensitive resin composition further contains (D) a colorant.

[11] A method for producing a cured product, comprising curing a photosensitive resin composition obtained by the method according to [9] or

[10] .

[12] A method for producing a black matrix, comprising forming a black matrix using a cured product obtained by the method according to

[11] .

[13] A method for producing an image display device, characterized by using a cured product obtained by the production method according to

[11] or a black matrix obtained by the production method according to

[12] .

[14] A method for controlling the molecular weight of a carboxyl group-containing resin, comprising: controlling the water content of a first reaction product A-containing liquid obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a second reaction product A-containing liquid; and adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid and reacting them to obtain a carboxyl group-containing resin.

[15] The method for controlling the molecular weight of a carboxyl group-containing resin according to

[14] , wherein water is added to the first reaction product A-containing liquid to control the moisture content of the first reaction product A-containing liquid so that the moisture content of the solution containing the second reaction product A-containing liquid is 0.1 mass % or more and 0.5 mass % or less, thereby obtaining the second reaction product A-containing liquid.

[16] The method for controlling the molecular weight of a carboxyl group-containing resin according to

[14] or

[15] , wherein the carboxyl group-containing resin is obtained by adding a polybasic acid dianhydride (c), a polybasic acid monoanhydride (d), and a polyhydric alcohol (e) to the second reaction product A-containing liquid and allowing them to react.

[17] The method for controlling the molecular weight of a carboxyl group-containing resin according to

[16] , wherein the polyhydric alcohol (e) contains trimethylolpropane.

[18] The method for controlling the molecular weight of a carboxy group-containing resin according to any one of

[14] to

[17] , wherein the polybasic acid dianhydride (c) includes biphenyltetracarboxylic dianhydride.

[19] The method for controlling the molecular weight of a carboxy group-containing resin according to any one of

[14] to

[18] , wherein the polybasic acid monoanhydride (d) includes tetrahydrophthalic anhydride. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for producing a carboxyl group-containing resin that allows control of the molecular weight and has excellent performance stability between production lots, and a method for controlling the molecular weight of a carboxyl group-containing resin. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing an example of an organic EL element provided with a color filter according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

[0013] In the present invention, the term "total solid content" refers to all components other than organic solvents and water contained in the photosensitive resin composition or the ink described below. In the present invention, the "photosensitive resin composition" may be referred to as a "resist." In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by gel permeation chromatography (GPC). In the present invention, unless otherwise specified, the "amine value" refers to the amine value calculated as the effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant. The measurement method will be described later.

[0014] [Method of manufacturing carboxyl group-containing resin] The method for producing a carboxyl group-containing resin of the present invention includes step A of reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a first reaction product A-containing liquid, step B of controlling the water content of the first reaction product A-containing liquid obtained in step A to obtain a second reaction product A-containing liquid, and step C of adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid obtained in step B and reacting them to obtain a carboxyl group-containing resin. The reaction product A contained in the first reaction product A-containing liquid obtained in step A can be considered an intermediate of the carboxyl group-containing resin, and may be referred to as the "intermediate" hereinafter. The reaction product A contained in the second reaction product A-containing liquid obtained in step B may also be referred to as the "intermediate" in the same manner. The reaction product A-containing liquid containing the first reaction product A-containing liquid and the second reaction product A-containing liquid may be a suspension, dispersion or solution as long as it is a liquid mixture containing reaction product A, and is preferably a reaction product A-containing solution.

[0015] <Process A> Step A is a step of synthesizing a reaction product A (intermediate) by reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent, and obtaining a first reaction product A-containing liquid containing the reaction product A.

[0016] The epoxy compound (a) is not particularly limited as long as it is a compound having an epoxy group. Examples thereof include bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828," "jER1001," "jER1002," "jER1004," etc., manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent: 323, softening point: 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resins (e.g., "jER807," "EP-4001," "EP- 4002, "EP-4004, etc."), epoxy resins obtained by reacting the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 350, softening point: 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" manufactured by Mitsubishi Chemical Corporation, EP-154, "DEN-438" manufactured by The Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (for example, "EOCN (registered trademark; the same applies hereinafter)-102S," "EOCN-1020," and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark; the same applies hereinafter)-501," "EPPN-502," and "EPPN Suitable examples of epoxy resins that can be used include alicyclic epoxy resins (Daicel Corporation's "Celloxide (registered trademark; the same applies hereinafter) 2021P" and "Celloxide EHPE"), epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, DIC Corporation's "EXA-7200" and Nippon Kayaku Co., Ltd.'s "NC-7300"), copolymers of epoxy group-containing (meth)acrylates and other radically polymerizable monomers, and epoxy compounds represented by the following general formulas (a1) to (a6). Specific examples of the epoxy compound represented by the following general formula (a1) include "XD-1000" manufactured by Nippon Kayaku Co., Ltd.; the epoxy compound represented by the following general formula (a2) includes "NC-3000" manufactured by Nippon Kayaku Co., Ltd.; and the epoxy compound represented by the following general formula (a4) includes "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0017] [ka]

[0018] In the general formula (a1), b11 represents an average value and is a number from 0 to 10. 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 11 may be the same or different from each other.

[0019] [ka]

[0020] In the general formula (a2), b12 represents an average value and is a number from 0 to 10. 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 21 may be the same or different from each other.

[0021] [ka]

[0022] In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2), provided that the molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0023] Among these, from the viewpoint of the patterning properties of the resist, X is preferably (a3-1) and b13 is preferably 2.

[0024] [ka]

[0025] In the above general formulae (a3-1) and (a3-2), R 31 ~R 34 and R 35 ~R 37 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group of 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. In the formula, * represents the bonding site in formula (a3).

[0026] From the viewpoint of resist patterning properties, formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms, and formula (3a-2) preferably has two adamantyl groups and one hydrogen atom.

[0027] [ka]

[0028] In the general formula (a4), p and q each independently represent an integer of 0 to 4; 41 and R 42 R each independently represents an alkyl group having 1 to 20 carbon atoms or a halogen atom. 43 and R 44 each independently represents an alkylene group having 1 to 5 carbon atoms, and x and y each independently represent an integer of 0 or greater.

[0029] Among these, p, q, x, and y are preferably 0 from the viewpoint of the patterning properties of the resist.

[0030] [ka]

[0031] In the above general formula (a5), R 51 ~R 54 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 56 are each independently an alkylene group having 1 to 5 carbon atoms, k is an integer of 1 to 5, l is an integer of 0 to 13, and each m is independently an integer of 0 to 5.

[0032] Among these, from the viewpoint of resist patterning properties, R 51 ~R 54 is preferably a hydrogen atom, k is preferably 2, and l and m are preferably 0.

[0033] [ka]

[0034] In the above general formula (a6), n and o each independently represent an integer of 1 to 9. R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 23 may be the same or different from each other.

[0035] Among these, from the viewpoint of resist patterning properties, it is preferable to use an epoxy compound represented by any one of general formulas (a1) to (a6), more preferably an epoxy compound represented by (a3), (a4), or (a5), and even more preferably an epoxy compound represented by (a5).

[0036] The unsaturated monobasic acid (b) may be any compound having only one acid group and one or more radically polymerizable unsaturated bonds in one molecule, and the acid group is preferably a carboxy group. By reacting the epoxy compound (a) with the unsaturated monobasic acid (b) in an organic solvent, the acid group reacts with the epoxy group of the epoxy compound to obtain a first reaction product A-containing liquid containing an intermediate in which a radically polymerizable double bond has been introduced into the epoxy compound.

[0037] Examples of the unsaturated monobasic acid (b) include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, α-substituted (meth)acrylic acid with haloalkyl, alkoxyl, halogen, nitro, and cyano groups, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, and 2-(meth)acryloyloxybutyl succinic acid. Examples of the monomer include 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, a monomer having one terminal carboxy group obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid, a monomer having one terminal hydroxyl group such as hydroxyalkyl (meth)acrylate, and a (meth)acrylic acid ester and (meth)acrylic acid dimer having one or more ethylenically unsaturated groups and one terminal carboxy group obtained by adding an acid (anhydride) such as (succinic anhydride), (phthalic anhydride), or (maleic anhydride to a compound having one terminal hydroxyl group such as pentaerythritol tri(meth)acrylate.

[0038] From the viewpoint of resist sensitivity and stability over time, the unsaturated monobasic acid (b) is preferably an alkenylcarboxylic acid, and more preferably (meth)acrylic acid.

[0039] Examples of organic solvents that can be used include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, and xylene. Among these, from the viewpoint of reaction yield, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferred, and propylene glycol monomethyl ether acetate is more preferred.

[0040] A known method can be used to react the epoxy compound (a) with the unsaturated monobasic acid (b) in an organic solvent to obtain an intermediate. For example, the epoxy compound (a) can be reacted with the unsaturated monobasic acid (b) in an organic solvent in the presence of a catalyst and a polymerization inhibitor at a temperature of 50 to 150°C.

[0041] Examples of the catalyst that can be used include tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride. Among these, tertiary phosphines are preferred, and triphenylphosphine is more preferred, from the viewpoint of reaction yield.

[0042] Examples of polymerization inhibitors that can be used include hydroquinone, methylhydroquinone, trimethylhydroquinone, paramethoxyphenol, and 2,6-di-tert-butyl-4-cresol. Among these, paramethoxyphenol and 2,6-di-tert-butyl-4-cresol are preferred, and paramethoxyphenol is more preferred, from the viewpoints of reaction yield and resist sensitivity.

[0043] The epoxy compound (a), unsaturated monobasic acid (b), organic solvent, catalyst and polymerization inhibitor may be used either individually or in combination of two or more.

[0044] The amount of unsaturated monobasic acid (b) used is preferably in the range of 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of epoxy compound (a), and more preferably in the range of 0.8 to 1.2 equivalents. By using the unsaturated monobasic acid (b) in an amount equal to or greater than the lower limit, the amount of residual epoxy is reduced, and gelation during the reaction with the polybasic acid anhydride in step B tends to be suppressed. Furthermore, by using the unsaturated monobasic acid (b) in an amount equal to or less than the upper limit, it tends to be suppressed that the unsaturated monobasic acid (b) remains unreacted.

[0045] <Process B> Step B is a step of controlling the water content of the first reaction product A-containing liquid obtained in step A to obtain a second reaction product A-containing liquid. By including step B in the method for producing a carboxyl group-containing resin of the present invention, it becomes possible to control the molecular weight of the carboxyl group-containing resin.

[0046] The method for controlling the water content of the first reaction product A-containing liquid obtained in step A is not particularly limited, but examples thereof include a method of adding water to the first reaction product A-containing liquid and a method of dehydrating the first reaction product A-containing liquid.

[0047] When water is added to the first reaction product A-containing liquid, water may be added alone or as a mixture of water and an organic solvent. The temperature of the first reaction product A-containing liquid at the time of addition is preferably 20°C to 80°C, more preferably 30°C to 70°C, even more preferably 40°C to 60°C, and particularly preferably 45°C to 55°C. By keeping the temperature within this range, water can be uniformly dispersed and dissolved in the first reaction product A-containing liquid. The addition of water to the first reaction product A-containing liquid is preferably carried out while stirring the first reaction product A-containing liquid, which allows the water to be uniformly dispersed and dissolved in the first reaction product A-containing liquid.

[0048] The amount of water added to the first reaction product A-containing liquid is preferably added so that the water content of the second reaction product A-containing liquid obtained in step B is 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.06% by mass or more, particularly preferably 0.1% by mass or more, and particularly preferably 0.18% by mass or more. Also, the water content is preferably 1% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less, particularly preferably 0.5% by mass or less, and particularly preferably 0.4% by mass or less. Setting the water content at or above the lower limit tends to reduce resist residue. Setting the water content at or below the upper limit tends to improve the stability of the resist over time. The upper and lower limits can be combined in any way. For example, 0.01 to 1 mass% is preferable, 0.03 to 0.8 mass% is more preferable, 0.06 to 0.6 mass% is even more preferable, 0.1 to 0.5 mass% is particularly preferable, and 0.18 to 0.4 mass% is particularly preferable.

[0049] Methods for dehydrating the first reaction product A-containing liquid include a method of drying using a porous material such as a molecular sieve or silica gel, or a dehydrating agent such as calcium chloride, and a method of distilling off the water under reduced pressure using a vacuum device. Among these, the method of distilling off the water under reduced pressure is preferred from the viewpoint of the purity and yield of the carboxyl group-containing resin. When distilling under reduced pressure, the pressure in the reaction vessel containing the first reaction product A-containing liquid is preferably 70 kPa or less, more preferably 60 kPa or less, even more preferably 50 kPa or less, and particularly preferably 40 kPa or less.

[0050] From the viewpoint of reaction time, step B preferably includes a step of adding water to the first reaction product A-containing liquid obtained in step A to control the water content of the first reaction product A-containing liquid, thereby obtaining a second reaction product A-containing liquid.

[0051] The moisture content of the reaction product A-containing liquid can be calculated by the Karl Fischer measurement method described in JIS K0113 (2005). Various moisture meters can be used, for example, the MKA-610 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0052] <Process C> Step C is a step of adding polybasic acid dianhydride (c) and polybasic acid monoanhydride (d) to the second reaction product A-containing liquid obtained in step B and reacting them to obtain a carboxy group-containing resin.

[0053] The polybasic acid dianhydride (c) may be any compound having only two acid anhydride groups in one molecule, and preferably contains a compound represented by general formula (c1) from the viewpoint of resist patterning properties.

[0054] [ka]

[0055] In the above formula (c1), A is a tetravalent organic group derived from a polybasic acid dianhydride.

[0056] Examples of the polybasic acid dianhydride (c) represented by general formula (c1) include biphenyltetracarboxylic dianhydride (BPDA), bicyclohexyltetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Among these, from the viewpoint of resist patterning properties, biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic anhydride are preferred, and biphenyltetracarboxylic dianhydride (BPDA) is more preferred.

[0057] The polybasic acid monoanhydride (d) may be any compound having only one acid anhydride group per molecule. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, and trimellitic anhydride can be used. Among these, from the viewpoint of resist patterning properties, succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are preferred, and tetrahydrophthalic anhydride is more preferred.

[0058] The polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d) may each be used alone or in combination of two or more.

[0059] A known method can also be used for the reaction of synthesizing a carboxyl group-containing resin by adding polybasic acid dianhydride (c) and polybasic acid monoanhydride (d) to the liquid containing the second reaction product A and reacting them. For example, the polybasic acid dianhydride (c) and polybasic acid monoanhydride (d) can be additionally added to the liquid containing the second reaction product A and reacted at a temperature of 50 to 150°C.

[0060] When the polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d) are added to the second reaction product A-containing solution and reacted, a polyhydric alcohol (e) may also be added and reacted. By further adding a polyhydric alcohol (e) and reacting it, a multi-branched structure can be introduced into the resulting carboxyl group-containing resin, improving the patterning properties of the resist.

[0061] Examples of the polyhydric alcohol (e) that can be used include trimethylolpropane, pentaerythritol, and dipentaerythritol. Among these, trimethylolpropane is preferred from the viewpoint of resist patterning properties.

[0062] The amount of polyhydric alcohol (e) used is preferably 0.01 equivalents or more, more preferably 0.03 equivalents or more, and even more preferably 0.05 equivalents or more, relative to 1 equivalent of unsaturated monobasic acid (b). Also, it is preferably 1 equivalent or less, more preferably 0.9 equivalents or less, and even more preferably 0.8 equivalents or less. By setting it to the lower limit or more, the stability of the resist over time tends to improve, and by setting it to the upper limit or less, the resist sensitivity tends to improve. The upper and lower limits can be combined in any way. For example, 0.01 to 1 equivalent is preferred, 0.03 to 0.9 equivalent is more preferred, and 0.05 to 0.8 equivalent is even more preferred.

[0063] The amount of polybasic acid dianhydride (c) used is preferably 0.1 equivalents or more, more preferably 0.3 equivalents or more, and even more preferably 0.5 equivalents or more, relative to 1 equivalent of polybasic acid monoanhydride (d). Also, it is preferably 50 equivalents or less, more preferably 30 equivalents or less, and even more preferably 10 equivalents or less. By setting it to the lower limit or more, the adhesion of the resist tends to be improved, and by setting it to the upper limit or less, the amount of resist residue tends to be reduced. The upper and lower limits can be combined arbitrarily. For example, the range is preferably 0.1 to 50 equivalents, more preferably 0.3 to 30 equivalents, and even more preferably 0.5 to 10 equivalents.

[0064] The acid value of the carboxyl group-containing resin produced by the method of the present invention is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, even more preferably 50 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. Also, it is preferably 250 mgKOH / g or less, more preferably 200 mgKOH / g or less, even more preferably 150 mgKOH / g or less, and particularly preferably 130 mgKOH / g or less. By setting it to the lower limit or more, resist residue tends to be reduced. Also, by setting it to the upper limit or less, resist adhesion tends to be improved. The upper and lower limits can be combined arbitrarily. For example, 10 to 250 mgKOH / g is preferable, 30 to 200 mgKOH / g is more preferable, 50 to 150 mgKOH / g is even more preferable, and 80 to 130 mgKOH / g is particularly preferable.

[0065] The weight-average molecular weight of the carboxyl group-containing resin produced by the production method of the present invention is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 8,000 or more, and particularly preferably 12,000 or more. Also, it is preferably 22,000 or less, more preferably 21,000 or less. By setting it to the lower limit or more, the adhesion of the resist tends to be improved. Also, by setting it to the upper limit or less, the amount of resist residue tends to be reduced. The upper and lower limits can be combined in any way. For example, 3,000 to 22,000 is preferable, 5,000 to 22,000 is more preferable, 8,000 to 21,000 is even more preferable, and 12,000 to 21,000 is particularly preferable.

[0066] [Carboxylic group-containing resin-containing liquid] The carboxyl group-containing resin-containing liquid obtained in step C contains a carboxyl group-containing resin, an organic solvent, and water. The water content of the obtained carboxyl group-containing resin-containing liquid is preferably 0.01% by mass or more and 1% by mass or less. By ensuring that the moisture content is within the above range, the residue of the resist using the carboxyl group-containing resin-containing liquid tends to be reduced, and the stability of the resist over time tends to be improved. The water content of the carboxyl group-containing resin-containing liquid is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more, even more preferably 0.06% by mass or more, particularly preferably 0.1% by mass or more, and particularly preferably 0.18% by mass or more. Also, it is more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less, particularly preferably 0.5% by mass or less, and particularly preferably 0.4% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.03% by mass or more and 0.8% by mass or less, more preferably 0.06% by mass or more and 0.6% by mass or less, more preferably 0.1% by mass or more and 0.5% by mass or less, and particularly preferably 0.18% by mass or more and 0.4% by mass or less. Setting it to the lower limit or more tends to reduce the residue of the resist using the resin solution. Setting it to the upper limit or less tends to improve the stability of the resist over time.

[0067] The carboxyl group-containing resin of the present invention contained in the carboxyl group-containing resin-containing liquid is preferably a carboxyl group-containing resin produced by the production method of the present invention. The carboxyl group-containing resin of the present invention preferably has a structure derived from the epoxy compound (a). The carboxyl group-containing resin of the present invention preferably has a structure derived from the unsaturated monobasic acid (b). The carboxyl group-containing resin of the present invention preferably has a structure derived from the polybasic acid dianhydride (c). The carboxyl group-containing resin of the present invention preferably has a structure derived from the polybasic acid monoanhydride (d). The carboxyl group-containing resin of the present invention preferably has a structure derived from the polyhydric alcohol (e). The preferred types and preferred blending amounts of the epoxy compound (a), the unsaturated monobasic acid (b), the polybasic acid dianhydride (c), the polybasic acid monoanhydride (d), and the polyhydric alcohol (e) are the same as the types and blending amounts described above.

[0068] As the organic solvent contained in the carboxyl group-containing resin-containing liquid, the organic solvent used in the method for producing the carboxyl group-containing resin of the present invention can be preferably used.

[0069] [Photosensitive resin composition] The method for producing a photosensitive resin composition of the present invention is a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and includes blending the carboxyl group-containing resin produced by the production method of the present invention as the alkali-soluble resin (A). The photosensitive resin composition produced by the production method of the present invention may also contain (D) a colorant.

[0070] <(A) Alkali-soluble resin> The photosensitive resin composition of the present invention contains, as the alkali-soluble resin (A), a carboxyl group-containing resin obtained by the production method of the present invention, and thus the performance stability between production lots is improved. The (A) alkali-soluble resin may contain other alkali-soluble resins.

[0071] The other alkali-soluble resin is not particularly limited as long as it changes the solubility in alkali development between the exposed and unexposed areas after exposure of the coating film obtained by coating and drying the photosensitive resin composition. However, alkali-soluble resins having a carboxy group are preferred. Those having an ethylenically unsaturated group are also preferred, and alkali-soluble resins having an ethylenically unsaturated group and a carboxy group are even more preferred. Specific examples include epoxy (meth)acrylate resins and acrylic copolymer resins having a carboxy group, such as the alkali-soluble resins described below as (A1-1), (A2-1), (A2-2), (A2-3), and (A2-4). These may be used alone or in combination of two or more. Among the above, epoxy (meth)acrylate resins having a carboxy group (A1-1) are particularly preferred.

[0072] When preparing a color filter, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphate group, or a sulfonic acid group is used as the polymer resin so that the non-exposed portion dissolves in an alkaline developer. Among these, a polymer resin having a carboxyl group is preferred from the viewpoint of solubility in an alkaline developer. Furthermore, although a phosphate group or a sulfonic acid group has a higher acidity than a carboxyl group, it is more likely to react with an initiator, a monomer, a dispersant, or other additives having a basic group in the photosensitive resin composition, which may result in poor storage stability.

[0073] An example of an epoxy(meth)acrylate resin having a carboxy group is the following epoxy(meth)acrylate resin (A1-1).

[0074] <Epoxy (meth)acrylate resin (A1-1)> An alkali-soluble resin obtained by adding an unsaturated monobasic acid to an epoxy compound and then reacting it with a polybasic acid monoanhydride.

[0075] <Epoxy (meth)acrylate resin (A1-1) having a carboxy group and an ethylenically unsaturated group bond> Examples of epoxy compounds that can be used as raw materials include bisphenol A epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark; the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004"), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "NER-1302" (epoxy equivalent: 323, softening point: 76°C)), and bisphenol F resins (e.g., Mitsubishi Chemical Corporation's " Epoxy resins obtained by reacting the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 350, softening point: 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EP-4001" manufactured by Nippon Kayaku Co., Ltd. (EP-4002" manufactured by Nippon Kayaku Co., Ltd.) PN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by The Dow Chemical Company, and "DEN-438" manufactured by The Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (for example, "EOCN (registered trademark; the same applies hereinafter)-102S," "EOCN-1020," and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd.), Suitable examples of epoxy resins that can be used include: epoxy resins such as "CELLOXIDE (registered trademark; the same applies hereinafter)-501," "EPPN-502," and "EPPN-503" manufactured by Daicel Corporation; alicyclic epoxy resins such as "CELLOXIDE (registered trademark; the same applies hereinafter)-2021P" and "CELLOXIDE EHPE" manufactured by Daicel Corporation; epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.); and epoxy resins represented by the following general formulas (a1) to (a6). Specific examples of epoxy resins represented by the following general formula (a1) include "XD-1000" manufactured by Nippon Kayaku Co., Ltd.; epoxy resins represented by the following general formula (a2) include "NC-3000" manufactured by Nippon Kayaku Co., Ltd.; and epoxy resins represented by the following general formula (a4) include "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0076] [ka]

[0077] In the general formula (a1), b11 represents an average value and is a number from 0 to 10. 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 11 may be the same or different from each other.

[0078] [ka]

[0079] In the general formula (a2), b12 represents an average value and is a number from 0 to 10. 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 21 may be the same or different from each other.

[0080] [ka]

[0081] In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2), provided that the molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0082] [ka]

[0083] In the above general formulae (a3-1) and (a3-2), R 31 ~R 34 and R 35 ~R 37 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group of 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. In the formula, * represents the bonding site in formula (a3). From the viewpoint of resist patterning properties, formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms, and formula (a3-2) preferably has two adamantyl groups and one hydrogen atom.

[0084] [ka]

[0085] In the general formula (a4), p and q each independently represent an integer of 0 to 4; 41 and R 42 R each independently represents an alkyl group having 1 to 20 carbon atoms or a halogen atom. 43 and R 44 each independently represents an alkylene group having 1 to 5 carbon atoms, and x and y each independently represent an integer of 0 or greater.

[0086] [ka]

[0087] In the above general formula (a5), R 51 ~R 54 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 55is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 56 are each independently an alkylene group having 1 to 5 carbon atoms, k is an integer of 1 to 5, l is an integer of 0 to 13, and each m is independently an integer of 0 to 5.

[0088] [ka]

[0089] In the above general formula (a6), n and o each independently represent an integer of 1 to 9. R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 23 may be the same or different from each other.

[0090] Among these, it is preferable to use an epoxy compound represented by any one of general formulas (a1), (a2) and (a6).

[0091] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, monocarboxylic acids such as (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, and cyano at the α-position, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, and 2-(meth)acryloyloxyethyl methyl acrylate. 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipate, 2-(meth)acryloyloxybutyl hydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, Examples of (meth)acrylic acid esters include monomers having one hydroxyl group at the terminal, which are obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid, and Alternatively, examples include (meth)acrylic acid esters and (meth)acrylic acid dimers having one or more ethylenically unsaturated groups and one terminal carboxy group, which are obtained by adding an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), or maleic acid (anhydride) to a monomer having one terminal hydroxyl group such as hydroxyalkyl (meth)acrylate, or a compound having one terminal hydroxyl group such as pentaerythritol tri(meth)acrylate.

[0092] Among these, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity. A known method can be used to add the unsaturated monobasic acid. For example, the unsaturated monobasic acid can be reacted with an epoxy compound in the presence of an esterification catalyst at a temperature of 50 to 150°C. Examples of the catalyst that can be used here include tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine; tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0093] The epoxy compound, unsaturated monobasic acid, and catalyst may each be used alone or in combination of two or more. The amount of unsaturated monobasic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the epoxy compound. By using an amount of the unsaturated monobasic acid that is equal to or greater than the lower limit, the amount of unsaturated groups introduced is sufficient, the subsequent reaction with the polybasic acid monoanhydride is also sufficient, and there is a tendency that a large amount of epoxy groups can be prevented from remaining. On the other hand, by using an amount that is equal to or less than the upper limit, there is a tendency that the unsaturated monobasic acid can be prevented from remaining as an unreacted product.

[0094] Examples of polybasic acid monoanhydrides include one or more selected from the group consisting of monoanhydrides of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, and methyltetrahydrophthalic acid.

[0095] Preferred are the anhydrides of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid, and particularly preferred is the monoanhydride of tetrahydrophthalic acid.

[0096] Known techniques can also be used for the addition reaction of polybasic acid monoanhydrides, and the target product can be obtained by continuing the reaction under conditions similar to those for the addition reaction of unsaturated monobasic acids to epoxy compounds. The amount of polybasic acid monoanhydride component added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g, more preferably in the range of 20 to 140 mg KOH / g. By adjusting the amount to be equal to or greater than the lower limit, alkaline developability tends to be improved. Meanwhile, by adjusting the amount to be equal to or less than the upper limit, curability tends to be improved.

[0097] The acid value of the epoxy (meth)acrylate resin (A1-1) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, and is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. By making the acid value equal to or greater than the lower limit, developability tends to be improved. On the other hand, by making the acid value equal to or less than the upper limit, alkali resistance tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the range is preferably 10 to 200 mgKOH / g, more preferably 50 to 200 mgKOH / g, and even more preferably 80 to 150 mgKOH / g.

[0098] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A1-1) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, and particularly preferably 2,500 or more. It is also preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 7,000 or less. By setting it to the lower limit or more, sensitivity, coating strength, and alkali resistance tend to be improved. By setting it to the upper limit or less, developability and resolubility tend to be improved. The upper and lower limits can be combined in any way. For example, 1,000 to 20,000 is preferable, 1,000 to 15,000 is more preferable, 1,500 to 10,000 is even more preferable, 2,000 to 8,000 is even more preferable, and 2,500 to 7,000 is particularly preferable.

[0099] <Acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4)> Examples of acrylic copolymer resins that can be used include various polymer compounds described in JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2007-270147. Preferred examples include resins (A2-1) to (A2-4) below, with resin (A2-1) being particularly preferred.

[0100] (A2-1): A resin obtained by adding an unsaturated monobasic acid to at least some of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, or a resin obtained by adding a polybasic acid monoanhydride to at least some of the hydroxyl groups generated by the addition reaction. (A2-2): A linear alkali-soluble resin containing a carboxyl group in the main chain. (A2-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of the (A2-2) resin. (A2-4): (Meth)acrylic resin.

[0101] From the viewpoint of sensitivity, the photosensitive resin composition of the present invention more preferably contains at least one of (A1-1), (A2-1), and (A2-3) as the alkali-soluble resin containing an ethylenically unsaturated group. From the viewpoint of surface curability, the photosensitive resin composition of the present invention particularly preferably contains (A1-1), an epoxy (meth)acrylate resin, as the alkali-soluble resin containing an ethylenically unsaturated group.

[0102] The content of the alkali-soluble resin (A) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, based on the total solids content of the photosensitive resin composition. By setting the content at or above the lower limit, the solubility of the unexposed areas in the developer tends to be improved. On the other hand, by setting the content at or below the upper limit, excessive penetration of the developer into the exposed areas can be suppressed, which tends to improve the sharpness and adhesion of the image. The upper and lower limits can be combined arbitrarily. For example, 5 to 90 mass % is preferable, 5 to 70 mass % is more preferable, 10 to 50 mass % is even more preferable, 10 to 30 mass % is still more preferable, and 15 to 25 mass % is particularly preferable. Furthermore, as described above, when the photosensitive resin composition of the present invention contains another alkali-soluble resin as the alkali-soluble resin (A), it is preferable that the other alkali-soluble resin contains at least one of the above-mentioned (A1-1), (A2-1), (A2-2), (A2-3) and (A2-4). When the photosensitive resin composition of the present invention contains other alkali-soluble resins, the content thereof is preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 10 mass % or less, based on the total amount of the alkali-soluble resins (A) from the viewpoint of resist patterning, and the composition may not contain any other alkali-soluble resins.

[0103] <(B) Photopolymerizable Monomer> The photosensitive resin composition of the present invention contains a photopolymerizable monomer (B) from the viewpoint of sensitivity and the like. Examples of the (B) photopolymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as "ethylenic monomers"). Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, and esters of carboxylic acids having one ethylenically unsaturated bond with polyhydric or monohydric alcohols.

[0104] As the (B) photopolymerizable monomer, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually two or more, preferably three or more, more preferably four or more, even more preferably five or more, and particularly preferably six or more, and is usually ten or less, preferably eight or less. By setting the number at or above the lower limit, the photosensitive resin composition tends to have high sensitivity, and by setting the number at or below the upper limit, curing shrinkage during polymerization tends to be small. The upper and lower limits can be combined in any way. For example, 2 to 10 is preferable, 3 to 10 is more preferable, 4 to 10 is even more preferable, 5 to 8 is even more preferable, and 6 to 8 is particularly preferable. Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0105] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate; and similarly, itaconic acid esters in which itaconate is replaced with itaconate, crotonate esters in which cronate is replaced with cronate, or maleate esters in which maleate is replaced with cronate.

[0106] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol, and glycerin.

[0107] Other useful examples of polyfunctional ethylenic monomers that can be used in the present invention include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. These may be used alone or in combination of two or more.

[0108] The content of the (B) photopolymerizable monomer is not particularly limited, but is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the total solid content of the photosensitive resin composition. When the content of the photopolymerizable monomer is equal to or less than the upper limit, the permeability of the developer into the exposed area tends to be adequate, and a good image tends to be obtained. The content of the photopolymerizable monomer (b) is usually 1% by mass or more, preferably 5% by mass or more. When the content is equal to or greater than the lower limit, the photocuring by ultraviolet irradiation tends to be improved and the alkali developability tends to be good. The above upper and lower limits can be combined in any manner, for example, 1 to 90 mass % is preferable, 1 to 70 mass % is more preferable, 1 to 50 mass % is even more preferable, 5 to 30 mass % is even more preferable, 5 to 20 mass % is particularly preferable, and 5 to 10 mass % is particularly preferable.

[0109] <(C) Photopolymerization initiator> The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. The photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and generates polymerization-active radicals. If necessary, an additive such as a sensitizing dye may be added to the photopolymerization initiator.

[0110] Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; radical activators and α-aminoalkylphenone derivatives such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters described in JP-A-10-39503; and oxime ester derivatives described in JP-A-2000-80068 and JP-A-2006-36750.

[0111] Examples of titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium Examples of the titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl].

[0112] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0113] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0114] Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0115] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0116] As the photopolymerization initiator, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are particularly useful in terms of sensitivity. Among oxime derivatives, oxime ester compounds are preferred in terms of adhesion to the substrate. When an alkali-soluble resin containing a phenolic hydroxyl group is used, it may be disadvantageous in terms of sensitivity.

[0117] Oxime ester-based photopolymerization initiators possess a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals. Therefore, they are highly sensitive even in small amounts and are stable against thermal reactions, making it possible to design highly sensitive photosensitive resin compositions with small amounts. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, oxime ester-based compounds containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) are more preferred because they exhibit this structural characteristic well. Currently, the market demands thin black matrices with high light blocking properties, and pigment concentrations are also increasing. Under these circumstances, these compounds are particularly effective.

[0118] Examples of the oxime ester compound include compounds containing a structural moiety represented by the following general formula (22), and preferably, the oxime ester compound represented by the following general formula (23).

[0119] [ka]

[0120] In the above formula (22), R 22 represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, each of which may be substituted.

[0121] [ka]

[0122] In formula (23), R 21a represents hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted. R 21b represents any substituent containing an aromatic ring or heteroaromatic ring.

[0123] In addition, R21a is R 21b and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) r -), polyethynylene group (-(C≡C) r -) or a group formed by combining these (wherein r is an integer of 0 to 3). R 22a is R in the above formula (22) 22 represents a group similar to the above. R in the above general formula (22) 22 and R in the above general formula (23) 22a As the alkanoyl group, preferred examples include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms.

[0124] R in the above general formula (23) 21a Preferred examples of the alkyl group include unsubstituted straight-chain alkyl groups or cycloalkylalkyl groups such as methyl, ethyl, and propyl groups, and propyl groups substituted with an N-acetyl-N-acetoxyamino group. In addition, R in the above general formula (23) 21b Preferred examples of the group include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenyl sulfide group.

[0125] The photopolymerization initiator of the oxime ester compound is R 21bFor the reasons mentioned above, an optionally substituted carbazolyl group is more preferred. Furthermore, a carbazole group having at least one group selected from the group consisting of an optionally substituted aryl group having 6 to 25 carbon atoms, an optionally substituted arylcarbonyl group having 7 to 25 carbon atoms, an optionally substituted heteroaryl group having 5 to 25 carbon atoms, an optionally substituted heteroarylcarbonyl group having 6 to 25 carbon atoms, and a nitro group is preferred. In particular, a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferred. Furthermore, it is desirable that these groups be bonded to the 3-position of the carbazolyl group.

[0126] Commercially available photopolymerization initiators of this type, which are oxime ester compounds, include OXE-02 manufactured by BASF, and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics Co., Ltd.

[0127] Specific examples of the photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but are not limited to these compounds.

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] Examples of the ketoxime ester compound include compounds containing a structural moiety represented by the following general formula (24), and preferably, the ketoxime ester compound represented by the following general formula (25).

[0132] [ka]

[0133] In the above general formula (24), R 24 has the same meaning as R22 in the general formula (22).

[0134] [ka]

[0135] In the above general formula (25), R 23a represents a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted.

[0136] R 23b represents any substituent containing an aromatic ring or heteroaromatic ring. In addition, R 23a is R 23b and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) r -), polyethynylene group (-(C≡C) r -) or a group formed by combining these (wherein r is an integer of 0 to 3).

[0137] R 24arepresents an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, each of which may be substituted. R in the above general formula (24) 24 and R in the above general formula (25) 24a Preferred examples of the alkanoyl group include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.

[0138] R in the above general formula (25) 23a Preferred examples of the alkyl group include an unsubstituted ethyl group, a propyl group, and a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group. In addition, R in the above general formula (25) 23b Preferred examples of the alkyl group include an optionally substituted carbazoyl group and an optionally substituted phenyl sulfide group. Specific examples of ketoxime ester compounds suitable for the present invention include the compounds exemplified below, but the present invention is not limited to these compounds.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] Commercially available photopolymerization initiators of such ketoxime ester compounds include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Strong Electronics Co., Ltd.

[0143] These oxime and ketoxime ester compounds are known per se and are one type of the series of compounds described in, for example, Japanese Patent Application Laid-Open Nos. 2000-80068 and 2006-36750. The photopolymerization initiators may be used alone or in combination of two or more.

[0144] Other examples include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropyl phenyl)propanone, and the like. acetophenone derivatives such as 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone. Among these photopolymerization initiators, oxime ester derivatives are particularly preferred for the reasons mentioned above.

[0145] <Sensitizing dye> The photopolymerization initiator may be used in combination with a sensitizing dye according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having heterocycles described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, and others, such as those described in JP-A-47-2528 and JP-A-54-155292.

[0044] Examples of dyes having a dialkylaminobenzene skeleton include those described in JP-B No. 45-37377, JP-A No. 48-84183, JP-A No. 52-112681, JP-A No. 58-15503, JP-A No. 60-88005, JP-A No. 59-56403, JP-A No. 2-69, JP-A No. 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, and JP-A No. 4-288818.

[0146] Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Examples include benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, and 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole. More preferred are p-dialkylaminophenyl group-containing compounds such as 4,4'-dialkylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, and particularly preferred is 4,4'-dialkylaminobenzophenone. The sensitizing dyes may be used alone or in combination of two or more.

[0147] The content of (C) photopolymerization initiator is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, based on the total solid content of the photosensitive resin composition, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. By setting it to be equal to or greater than the lower limit, sensitivity tends to be improved. On the other hand, by setting it to be equal to or less than the upper limit, solubility of the unexposed portion in the developer tends to be improved. The upper and lower limits can be combined arbitrarily. For example, 1 to 30 mass % is preferable, 1 to 20 mass % is more preferable, 2 to 15 mass % is even more preferable, 3 to 10 mass % is even more preferable, and 4 to 8 mass % is particularly preferable.

[0148] When a sensitizing dye is used, the blending ratio of the sensitizing dye in the photosensitive resin composition is usually 0 to 20 mass %, preferably 0 to 15 mass %, and more preferably 0 to 10 mass %, of the total solid content in the photosensitive resin composition.

[0149] <(D) Color material> When the photosensitive resin composition of the present invention is used to form pixels, black matrices, colored spacers, etc. of a color filter, it preferably contains a colorant (D). The colorant refers to a material that colors the photosensitive resin composition of the present invention. As the colorant, dyes and pigments can be used, but pigments are preferred from the viewpoints of heat resistance, light resistance, etc.

[0150] Pigments of various colors can be used, such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments, etc. In addition to organic pigments with azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based structures, various inorganic pigments can also be used.

[0151] Specific examples of pigments that can be used in the present invention are shown below by pigment number. Note that terms such as "CI Pigment Red 2" listed below refer to the Color Index (CI). Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53:3. :3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 300, 301, 302, 303, 304, 305, 306, 307, 35, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, and 276. Of these, preferred are CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254, and more preferred are CI Pigment Red 177, 209, 224, and 254.

[0152] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI Pigment Blue 15:6 and 60 are more preferred.

[0153] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Of these, CI Pigment Green 7, 36, and 58 are preferred.

[0154] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, and 134. , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferred, and CI Pigment Yellow 83, 138, 139, 150, and 180 are more preferred.

[0155] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Of these, CI Pigment Orange 38, 64, and 71 are preferred.

[0156] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19, 23, and 29 are preferred, and CI Pigment Violet 23 and 29 are more preferred.

[0157] When the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black colorant can be used as the colorant (D). The black colorant may be a single black colorant or a mixture of red, green, blue, and other colorants. These colorants can be appropriately selected from inorganic or organic pigments and dyes. Examples of colorants that can be mixed to prepare black colorants include Victoria Pure Blue (42595), Auramine O (41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), and Shimla First Yellow. -8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionor Red 7B4401 (15850), Firstgen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15:6), Lionor Red GD (Pigment Red 168), and Lionor Green 2YS (Pigment Green 36) (Note: The numbers in parentheses above refer to the Color Index (CI)).

[0158] Further, other pigments that can be mixed and used, shown by CI number, include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61, 64; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; CI violet pigments 19, 23, 29, 30, 37, 40, 50; CI blue pigments 15, 15:1, 15:4, 22, 60, 64; CI green pigment 7; and CI brown pigments 23, 25, 26.

[0159] Examples of black coloring materials that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black. When a black coloring material is used among these coloring materials (D), carbon black is preferred from the viewpoint of light blocking rate and image characteristics. Examples of carbon black include the following carbon blacks.

[0160] Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Manufactured by Degussa: Printex (registered trademark. The same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Cabot Corporation: Monarch (registered trademark; the same applies hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark; the same applies hereinafter) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8 Biller: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0161] Other examples of black pigments include titanium black, aniline black, iron oxide black pigments, and a mixture of three organic pigments of red, green, and blue colors that can be used as the black pigment.

[0162] Examples of pigments that can be used include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. These pigments can also be used in combination. For example, to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination.

[0163] The average particle size of the pigment is not particularly limited as long as it can produce the desired color when used in a colored layer of a color filter, and although it varies depending on the type of pigment used, it is preferably in the range of 10 to 100 nm, more preferably in the range of 10 to 70 nm. When the average particle size of the pigment is in the above range, the color characteristics of a liquid crystal display device manufactured using the photosensitive resin composition of the present invention tend to be of high quality. The average particle size of carbon black is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more, for example, preferably 20 to 50 nm, more preferably 20 to 60 nm. By setting the average particle size to the above upper limit or less, scattering tends to be reduced, and deterioration of color properties such as light-blocking ability and contrast tends to be suppressed. Furthermore, by setting the average particle size to the above lower limit or more, the amount of dispersant does not need to be excessively large, and dispersibility tends to be good. The average particle size of the above pigments, including carbon black, can be determined by directly measuring the size of primary particles from electron microscope photographs. Specifically, the minor and major axis diameters of each primary particle are measured, and the average is taken as the particle size of that particle. Next, the volume (mass) of each of 100 or more particles is determined by approximating it to a rectangular parallelepiped of the determined particle size, and the volume-average particle size is determined, which is taken as the average particle size. The same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0164] When the photosensitive resin composition of the present invention contains a colorant (D), it is preferable that the colorant contains at least a pigment, but other dyes may be used in combination as long as they do not affect the effects of the present invention. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0165] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0166] Examples of anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60. Other examples of phthalocyanine dyes include CI Pad Blue 5; quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9; quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64; and nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0167] When the photosensitive resin composition of the present invention contains a colorant (D), the content of the colorant (D) can be selected from the range of usually 1 to 70% by mass based on the total solid content in the photosensitive resin composition. Within this range, 20% by mass or more is more preferable, 30% by mass or more is even more preferable, 40% by mass or more is particularly preferable, and 60% by mass or less is more preferable. The upper and lower limits can be combined arbitrarily. For example, 1 to 70 mass % is preferred, 20 to 70 mass % is more preferred, 30 to 60 mass % is even more preferred, and 40 to 60 mass % is particularly preferred.

[0168] The photosensitive resin composition of the present invention can be used for various purposes as described below, but when used to form a black matrix, the (D) colorant may be a black colorant such as the above-mentioned carbon black or titanium black, or a mixture of multiple types of colorants other than black may be used to adjust the color to black. Among these, carbon black is particularly preferred from the viewpoints of dispersion stability and light-shielding properties.

[0169] When the photosensitive resin composition of the present invention is used to form a black matrix, it is necessary to increase the concentration of the black colorant to increase the light-shielding effect. From this viewpoint, the content of the black colorant is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more, based on the total solid content of the photosensitive resin composition. Furthermore, from the viewpoint of image forming performance, it is preferably 70% by mass or less, and more preferably 65% ​​by mass or less. The upper and lower limits can be combined arbitrarily. For example, the content is preferably 40 to 70 mass %, more preferably 45 to 70 mass %, and even more preferably 50 to 65 mass %.

[0170] When the photosensitive resin composition of the present invention contains a (D) colorant, the content of the (D) colorant per 100 parts by mass of the (A) alkali-soluble resin is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, even more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, and most preferably 160 parts by mass or more, and is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 280 parts by mass or less. By setting the content of the (D) colorant at or above the lower limit, it is easy to suppress a decrease in the solubility of the unexposed area in the developer. On the other hand, by setting the content at or below the upper limit, it is easy to obtain a desired image film thickness. The upper and lower limits can be combined in any way. For example, 20 to 500 parts by mass is preferable, 30 to 500 parts by mass is more preferable, 40 to 500 parts by mass is even more preferable, 60 to 300 parts by mass is even more preferable, 80 to 300 parts by mass is particularly preferable, 120 to 280 parts by mass is particularly preferable, and 160 to 280 parts by mass is most preferable.

[0171] <Dispersant> When the photosensitive resin composition of the present invention contains a colorant (D), it is important to finely disperse the colorant and stabilize the dispersed state in order to ensure stable quality, and therefore it is preferable that the composition further contains a dispersant. As the dispersant, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as a carboxyl group; a phosphate group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferred. Among these, a polymer dispersant having a basic functional group such as a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is particularly preferred. The use of a polymer dispersant having such a basic functional group tends to improve dispersibility.

[0172] Examples of polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of a monomer and a macromonomer having an amino group, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants.

[0173] Specific examples of such dispersants include, by trade name, EFKA (registered trademark, manufactured by EFKA Chemicals BV), Disperbyk (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Inc.). These polymer dispersants may be used alone or in combination of two or more.

[0174] Among these, from the viewpoints of adhesion and linearity, the dispersant preferably contains a urethane-based polymer dispersant and / or an acrylic-based polymer dispersant having a basic functional group, and from the viewpoint of adhesion, the dispersant containing a urethane-based polymer dispersant is more preferable.Furthermore, from the viewpoints of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester and / or polyether bond is preferable.

[0175] The weight-average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100000 or less, preferably 50000 or less, and more preferably 30000 or less. By setting it to the above upper limit or less, alkaline developability tends to be good even when the pigment concentration is high. The upper and lower limits can be combined arbitrarily. For example, 700 to 100,000 is preferable, 700 to 50,000 is more preferable, and 1,000 to 30,000 is even more preferable. Examples of urethane-based and acrylic polymer dispersants include the Disperbyk 160 to 167 and 182 series (all urethane-based), and Disperbyk 2000 and 2001 (all acrylic-based) (all manufactured by BYK-Chemie). Particularly preferred examples of the urethane-based polymer dispersants having a basic functional group and a polyester and / or polyether bond and a weight-average molecular weight of 30,000 or less include Disperbyk 167 and 182.

[0176] <Urethane-based polymer dispersant> Specific examples of chemical structures preferred for urethane-based polymer dispersants include dispersion resins with a weight average molecular weight of 1,000 to 200,000 obtained by reacting a polyisocyanate compound with a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000, and a compound having an active hydrogen and a tertiary amino group in the same molecule.

[0177] Examples of the polyisocyanate compound include aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and ω,ω'-dimethyl diisocyanate. Examples of suitable polyisocyanates include alicyclic diisocyanates such as cyclohexane, aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate, and their trimers, water adducts, and polyol adducts. Preferred polyisocyanates are trimers of organic diisocyanates, with the most preferred being the trimer of tolylene diisocyanate and the trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

[0178] Examples of methods for producing isocyanate trimers include a method in which the polyisocyanates are subjected to partial trimerization of isocyanate groups using an appropriate trimerization catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, or carboxylates, and the trimerization is terminated by adding a catalyst poison. Thereafter, the unreacted polyisocyanate is removed by solvent extraction or thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

[0179] Examples of compounds having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these.

[0180] Examples of polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more thereof.

[0181] Examples of polyetherester diols include those obtained by reacting an ether group-containing diol or a mixture thereof with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, such as poly(polyoxytetramethylene) adipate. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0182] Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, Examples of polyester glycols include those obtained by polycondensation of aliphatic glycols such as hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and N-alkyldialkanolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate; and polylactone diols or polylactone monools obtained using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol and polymethylvalerolactone, and mixtures of two or more thereof. The most preferred polyester glycols are polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

[0183] Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.

[0184] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000. Next, we will explain compounds having active hydrogen and a tertiary amino group in the same molecule. Active hydrogen, i.e., a hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom, includes hydrogen atoms in functional groups such as hydroxyl groups, amino groups, and thiol groups, and among these, a hydrogen atom in an amino group, particularly a primary amino group, is preferred.

[0185] The tertiary amino group is not particularly limited, but examples thereof include an amino group having an alkyl group with 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring. Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0186] When the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include N-containing 5-membered heterocyclic rings such as a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring, and nitrogen-containing 6-membered heterocyclic rings such as a pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

[0187] Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. Of these, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole are preferred.

[0188] These may be used alone or in combination of two or more. The preferred blending ratio of raw materials when producing a urethane-based polymer dispersant is 100 parts by mass of polyisocyanate compound, 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule.

[0189] The production of urethane polymer dispersants is carried out according to known methods for producing polyurethane resins. Examples of solvents used in the production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, sec-butanol, and tert-butanol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0190] In the above production, a urethanization reaction catalyst is usually used, and examples of this catalyst include one or more of tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0191] <Method for measuring amine value> The tertiary amine value of a dispersant is expressed as the mass of KOH equivalent to the amount of base per gram of solids excluding the solvent in a dispersant sample, and can be measured by the following method. Accurately weigh out 0.5-1.5 g of dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize this solution with a 0.1 mol / L HClO4 (perchloric acid) acetic acid solution. The inflection point on the titration pH curve is used as the titration endpoint, and the amine value is calculated using the following formula.

[0192] Amine value [mgKOH / g] = (561 × V) / (W × S) (W: weight of dispersant sample [g], V: titration volume at the end of titration [mL], S: solids concentration of the dispersant sample [mass %].) The amount of the compound having an active hydrogen and a tertiary amino group introduced in the same molecule is preferably controlled to a range of 1 to 100 mg KOH / g in terms of amine value after reaction, more preferably 5 to 95 mg KOH / g. The amine value is a value obtained by neutralizing titration of a basic amino group with an acid, and expressed in mg of KOH corresponding to the acid value. By setting the amine value at or above the lower limit, dispersibility tends to be improved. On the other hand, by setting the amine value at or below the upper limit, developability tends to be improved.

[0193] If isocyanate groups remain in the polymer dispersant after the above reaction, it is preferable to further consume the isocyanate groups with an alcohol or an amino compound, as this increases the stability of the product over time. The weight-average molecular weight (Mw) of the urethane polymer dispersant is typically in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. It is particularly preferably 30,000 or less. Setting it above the lower limit tends to improve dispersibility and dispersion stability. Setting it below the upper limit tends to improve solubility. The upper and lower limits can be arbitrarily combined. For example, it may be 1,000 to 30,000, 2,000 to 30,000, or 3,000 to 30,000. A molecular weight of 30,000 or less tends to improve alkaline developability, even when the pigment concentration is particularly high. Examples of such particularly preferred commercially available urethane dispersants include Disperbyk 167 and 182 (BYK-Chemie).

[0194] When the photosensitive resin composition of the present invention contains a dispersant, the content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, the content is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass. The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of the (D) colorant. The above upper and lower limits can be arbitrarily combined. For example, 5 to 200 parts by mass is preferred, 10 to 80 parts by mass is more preferred, and 15 to 50 parts by mass is even more preferred. By adjusting the content to be equal to or greater than the lower limit, sufficient dispersibility tends to be ensured, while by adjusting the content to be equal to or less than the upper limit, sufficient color density, sensitivity, film-forming properties, etc. tend to be achieved without reducing the proportions of other components.

[0195] <Thiols> The photosensitive resin composition of the present invention preferably contains a thiol in order to improve sensitivity and adhesion to a substrate. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane (trade name: Karenz MT). BD1, manufactured by Showa Denko K.K.), butanediol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate); (trade name: Karenz MT PE1, manufactured by Showa Denko K.K.), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko K.K. Various types of these can be used alone or in combination of two or more. Polyfunctional thiols such as PGMB, TPMB, TPMIB, KarenzMT BD1, KarenzMT PE1, and KarenzMT NR1 are preferred, and among these, KarenzMT BD1, KarenzMT PE1, and KarenzMT NR1 are more preferred, and KarenzMT PE1 is particularly preferred.

[0196] When a thiol compound is used, the content of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention, and is usually 10% by mass or less, preferably 5% by mass or less. By setting the content at or above the lower limit, sensitivity deterioration tends to be suppressed. Meanwhile, by setting the content at or below the upper limit, storage stability tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the content is preferably 0.1 to 10 mass %, more preferably 0.3 to 10 mass %, and even more preferably 0.5 to 5 mass %.

[0197] <Solvent> The photosensitive resin composition of the present invention is generally used in a state in which various materials including (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a colorant, which is used as needed, are dissolved or dispersed in an organic solvent. As the solvent, the organic solvent used in the production method of the present invention or the organic solvent contained in the carboxy group-containing resin-containing liquid of the present invention may be used as it is. The organic solvent to be selected preferably has a boiling point (under a pressure of 1013.25 [hPa]; the same applies to all boiling points hereinafter) in the range of 100 to 300°C. A solvent with a boiling point of 120 to 280°C is more preferred. Examples of such organic solvents include the following:

[0198] glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0199] glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0200] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0201] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0202] Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Examples of commercially available solvents that fall under the above category include mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark; the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all of which are trade names).

[0203] These organic solvents may be used alone or in combination of two or more kinds. When forming pixels or black matrices of a color filter by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250°C, more preferably 120 to 230°C. Of the above organic solvents, glycol alkyl ether acetates are preferred because they have a good balance of coating properties, surface tension, etc., and the solubility of the components in the composition is relatively high.

[0204] Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as other organic solvents that may be used in combination. Among these, propylene glycol monomethyl ether is particularly preferred due to its ability to dissolve the components in the composition. Glycol monoalkyl ethers have high polarity, and if added in excessive amounts, the colorant tends to aggregate, increasing the viscosity of the resulting photosensitive resin composition and otherwise reducing storage stability. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

[0205] It is also preferable to use an organic solvent with a boiling point of 200°C or higher (hereinafter sometimes referred to as a "high-boiling solvent"). The use of such a high-boiling solvent makes the photosensitive resin composition less likely to dry, but also prevents the uniform dispersion of the colorant in the composition from being destroyed by rapid drying. In other words, it is effective in preventing the occurrence of foreign matter defects due to precipitation and solidification of the colorant, for example, at the tip of a slit nozzle. Among the various solvents mentioned above, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate are particularly preferred due to their high effectiveness.

[0206] The content of the high-boiling point solvent in the organic solvent is preferably 0% to 50% by mass, more preferably 0.5% to 40% by mass, and particularly preferably 1% to 30% by mass. By ensuring that the content is equal to or greater than the lower limit, it is possible to prevent, for example, the coloring material from precipitating and solidifying at the tip of the slit nozzle, which can cause foreign matter defects. Furthermore, by ensuring that the content is equal to or less than the upper limit, it is possible to slow down the drying temperature of the composition, which can prevent problems in the color filter manufacturing process, such as poor tact time in the reduced-pressure drying process and pin marks during pre-baking.

[0207] In the photosensitive resin composition of the present invention, the content ratio of the organic solvent is not particularly limited. However, from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0208] <Other ingredients of the photosensitive resin composition> In addition to the above-mentioned components, the photosensitive resin composition of the present invention may contain, as appropriate, adhesion improvers, coating property improvers, pigment derivatives, development improvers, ultraviolet absorbers, antioxidants, and the like.

[0209] <Adhesion improver> To improve adhesion to the substrate, an adhesion promoter may be added, for example, a silane coupling agent or a titanium coupling agent, with the silane coupling agent being particularly preferred. Examples of such silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shin-Etsu Silicones Co., Ltd.), and Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., Ltd.) The silane coupling agents may be used alone or in any combination and ratio of two or more. Furthermore, an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include phosphoric acid-based adhesion improvers and other adhesion improvers.

[0210] As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferred, and among them, those represented by the following general formulas (g1), (g2) and (g3) are preferred.

[0211] [ka]

[0212] In the above general formulae (g1), (g2) and (g3), R51 each independently represents a hydrogen atom or a methyl group, l and l' each independently represents an integer of 1 to 10, and m each independently represents 1, 2 or 3. Other adhesion improvers include TEGO*Add Bond LTH (manufactured by Evonik), etc. These phosphate group-containing compounds and other adhesion improvers may be used alone or in combination of two or more.

[0213] When the photosensitive resin composition of the present invention contains an adhesion improver, the content of the adhesion improver in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, based on the total solid content of the photosensitive resin composition. By setting the content at or above the lower limit, adhesion tends to be improved. On the other hand, by setting the content at or below the upper limit, developability tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the content is preferably 0.01 to 5 mass%, more preferably 0.01 to 3 mass%, even more preferably 0.1 to 2 mass%, and particularly preferably 0.5 to 1.5 mass%.

[0214] <Coating improver> The photosensitive resin composition of the present invention may contain a surfactant as a coatability improver to improve coatability. Examples of surfactants that can be used include anionic, cationic, nonionic, and amphoteric surfactants. Among these, nonionic surfactants are preferred because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are particularly effective in terms of coatability.

[0215] Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M Japan Co., Ltd.) The surfactants may be used alone or in any combination and ratio of two or more. When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant in the photosensitive resin composition is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and preferably 1.0 mass% or less, more preferably 0.7 mass% or less, even more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, based on the total solid content of the photosensitive resin composition. By setting the content at or above the lower limit, the resist coating uniformity tends to improve. On the other hand, by setting the content at or below the upper limit, the resist sensitivity tends not to decrease. The upper and lower limits can be combined arbitrarily. For example, the range is preferably 0.01 to 1.0 mass%, more preferably 0.01 to 0.7 mass%, even more preferably 0.05 to 0.5 mass%, and particularly preferably 0.05 to 0.3 mass%.

[0216] <Pigment derivatives> The photosensitive resin composition of the present invention may contain a pigment derivative to improve dispersibility and storage stability. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinophthalone-based derivatives being preferred.

[0217] Examples of substituents on pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, and the like, with sulfonic acid groups being preferred. Furthermore, a single pigment skeleton may be substituted with a plurality of these substituents. Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0218] When the photosensitive resin composition of the present invention contains a pigment derivative, the blending ratio of the pigment derivative is not particularly limited, but is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and even more preferably 1.0 mass % or more, based on the total solid content of the photosensitive resin composition, and is preferably 10 mass % or less, more preferably 5 mass % or less. By making the blending ratio equal to or greater than the lower limit, dispersion stability tends to be improved. On the other hand, by making the blending ratio equal to or less than the upper limit, developability tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the range is preferably 0.1 to 10 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1.0 to 5 mass %.

[0219] <Physical properties of photosensitive resin composition> The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from this viewpoint, it is preferable that it exhibits a black color. The optical density (OD) per μm of film thickness of the coating film is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 2.5 or more, even more preferably 3.0 or more, particularly preferably 4.0 or more, most preferably 4.5 or more, and usually 6.0 or less, for example, preferably 1.0 to 6.0, more preferably 2.0 to 6.0, even more preferably 2.5 to 6.0, even more preferably 3.0 to 6.0, particularly preferably 4.0 to 6.0, and most preferably 4.5 to 6.0. By ensuring that the OD is equal to or greater than the lower limit, sufficient light-shielding properties tend to be ensured.

[0220] <Method for producing photosensitive resin composition> When the photosensitive resin composition of the present invention contains a (D) colorant, the (D) colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. The dispersion process microparticulates the (D) colorant, improving the coating properties of the resist. Furthermore, when a black colorant is used as the (D) colorant, this contributes to improving the light-shielding ability.

[0221] The dispersion treatment is preferably carried out in a system that combines (D) a colorant, an organic solvent, and, if necessary, a dispersant, and part or all of (A) an alkali-soluble resin. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as "ink" or "pigment dispersion.") In particular, using a polymer dispersant as the dispersant is preferred because it inhibits the resulting ink and resist from thickening over time (leading to excellent dispersion stability). When a dispersion treatment is performed on a liquid containing all the components to be blended into the photosensitive resin composition, the heat generated during the dispersion treatment may cause denaturation of highly reactive components. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

[0222] When dispersing the (D) colorant using a sand grinder, glass beads or zirconia beads with a diameter of approximately 0.1 to 8 mm are preferably used. Regarding dispersion conditions, the temperature is typically between 0°C and 100°C, preferably between room temperature and 80°C. The dispersion time varies depending on the liquid composition and the size of the dispersion treatment device, so it should be adjusted as appropriate. A guideline for dispersion is to control the gloss of the ink so that the 20° specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. If the resist has low gloss, the dispersion treatment is often insufficient, leaving coarse pigment (colorant) particles, which can result in insufficient developability, adhesion, resolution, and other properties. Furthermore, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed, producing a large number of ultrafine particles, which tends to actually impair dispersion stability.

[0223] Next, the components contained in the photosensitive resin composition, i.e., (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) colorant, if present, are blended with the ink obtained by the above dispersion treatment and mixed at a temperature of 20 to 30° C. to form a uniform solution. Since fine dust particles are often mixed in the liquid during the production process of the photosensitive resin composition, it is desirable to filter the obtained resist using a filter or the like.

[0224] [ink] The ink production method of the present invention is a method for producing an ink containing (A) an alkali-soluble resin, an organic solvent, and (D) a colorant, and includes blending a carboxyl group-containing resin produced by the production method of the present invention as the alkali-soluble resin (A).The ink may also contain a dispersant, if necessary. As the organic solvent, (D) coloring material and dispersant, those used in the photosensitive resin composition can be preferably used.

[0225] <Ink manufacturing method> The ink of the present invention can be obtained, for example, by the dispersion treatment described in the method for producing the photosensitive resin composition.

[0226] [Cured product] The method for producing a cured product of the present invention includes curing the photosensitive resin composition obtained by the production method of the present invention. A cured product obtained by curing the photosensitive resin composition can be suitably used as a component for a color filter, such as a pixel, a black matrix, or a colored spacer.

[0227] [Black Matrix] The method for producing a black matrix of the present invention includes forming a black matrix using the cured product obtained by the production method of the present invention. A black matrix using the cured product obtained by the production method of the present invention will be described in accordance with the production method.

[0228] (1) Support The material of the support for forming the black matrix is ​​not particularly limited as long as it has adequate strength. Transparent substrates are mainly used, and examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass. Among these, glass and heat-resistant resins are preferred from the viewpoint of heat resistance. Furthermore, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. It is also possible to form the black matrix on a substrate other than a transparent substrate, for example, a TFT array.

[0229] In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, or thin film formation treatment using a silane coupling agent or various resins such as urethane resins, as necessary. The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film of various resins is formed, the thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0230] (2) Black matrix A method for forming a black matrix using the cured product obtained by the production method of the present invention includes a method for forming a black matrix using the cured product obtained by curing the photosensitive resin composition obtained by the production method of the present invention. For example, there is a method for forming a black matrix using the cured product obtained by curing the photosensitive resin composition of the present invention, which is applied to a transparent substrate and dried, and then a photomask is placed on the dried sample, and the composition is imagewise exposed through the photomask, developed, and optionally thermally or photocured to form a black matrix.

[0231] (3) Formation of black matrix (3-1) Coating of photosensitive resin composition The photosensitive resin composition for a black matrix can be applied to a transparent substrate by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among these, the die coating method is preferred from an overall viewpoint, since it significantly reduces the amount of coating solution used, is completely free from the influence of mist or the like that adheres when using a spin coating method, and suppresses the generation of foreign matter.

[0232] The thickness of the coating film after drying is preferably in the range of 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. By setting the thickness at or below the upper limit, pattern development tends to be easy, and gap adjustment in the liquid crystal cell fabrication process also tends to be easy. By setting the thickness at or above the lower limit, desired color expression tends to be easy.

[0233] (3-2) Drying of the coating After applying the photosensitive resin composition to the substrate, the coating film is preferably dried using a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. Drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200°C, and preferably within the range of 30 seconds to 3 minutes at a temperature of 50 to 130°C, depending on the type of solvent component, the performance of the dryer used, etc.

[0234] The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but if the temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and resulting in poor development. The drying process of this coating film may also be a reduced-pressure drying method in which drying is carried out in a reduced-pressure chamber without increasing the temperature.

[0235] (3-3) Exposure Imagewise exposure is carried out by superimposing a negative mask pattern on a coating film of the photosensitive resin composition and irradiating the film with light having a wavelength ranging from the ultraviolet region to the visible region through the mask pattern. If necessary, an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film before exposure to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen. The light source used for the imagewise exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. When using light of a specific wavelength, an optical filter can also be used.

[0236] (3-4) Development The black matrix of the present invention can be prepared by imagewise exposing a coating film of the photosensitive resin composition to the above-mentioned light source, followed by development using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound to form an image on a substrate. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0237] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used alone or in combination.

[0238] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkylbetaines and amino acids.

[0239] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution. The conditions for the development treatment are not particularly limited. The development temperature is usually in the range of 10 to 50°C, preferably 15 to 45°C, and particularly preferably 20 to 40°C. The development method can be any of immersion development, spray development, brush development, ultrasonic development, and the like.

[0240] (3-5) Heat curing treatment After development, the substrate is subjected to a heat curing treatment or a photocuring treatment, preferably a heat curing treatment, in which the heat curing treatment conditions are selected from the temperature range of 100 to 280°C, preferably from 150 to 250°C, and the time range of 5 to 60 minutes. The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm. Furthermore, the optical density (OD) per 1 μm of thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.

[0241] [Formation of other color filters] A photosensitive resin composition containing a colorant of one of red, green, and blue colors is applied to a transparent substrate provided with a black matrix using the same processes as those described above in (3-1) to (3-5). After drying, a photomask is placed on the coating film, and a pixel image is formed by imagewise exposure through the photomask, development, and, if necessary, heat or light curing to form a colored layer. This process is repeated for each of the photosensitive resin compositions of red, green, and blue colors, thereby forming a color filter. The order of these processes is not limited to the above.

[0242] [Colored spacer] The photosensitive resin composition obtained by the production method of the present invention can also be used as a resist for colored spacers in addition to black matrices. When spacers are used in TFT-type LCDs, light incident on the TFTs can cause the TFTs to malfunction as switching elements, and colored spacers are used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 describes making spacers light-blocking. Colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.

[0243] (3-6) Formation of transparent electrodes Color filters are used as they are, with a transparent electrode such as ITO formed on the image, as part of components for color displays, liquid crystal display devices, etc. However, to improve surface smoothness and durability, a topcoat layer of polyamide, polyimide, etc. can be formed on the image as needed. In some applications, such as in planar alignment driving systems (IPS mode), a transparent electrode may not be formed.

[0244] [Bulkhead] The photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention can also be used to form partition walls, particularly partition walls for separating organic layers of organic electroluminescent devices. Examples of organic layers used in organic electroluminescent devices include organic layers used as hole injection layers, hole transport layers, or hole transport layers on hole injection layers, as described in JP 2016-165396 A.

[0245] The photosensitive resin composition obtained by the production method of the present invention or the partition wall using the photosensitive resin composition of the present invention will be described according to the production method.

[0246] (4-1) Support As the support and substrate for forming the partition walls, the same support and substrate as those for forming the black matrix can be used.

[0247] (4-2) Bulkhead Hereinafter, the case of use as a partition wall will be described with reference to specific examples of a method for forming a partition wall using the photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention.

[0248] Typically, a photosensitive resin composition is applied in the form of a film or a pattern by coating or other methods onto a substrate on which partition walls are to be formed, and the solvent is dried. Subsequently, a pattern is formed by a method such as photolithography, which involves exposure and development. Thereafter, if necessary, additional exposure or heat curing treatment is carried out to form the partition walls on the substrate.

[0249] (4-3) Formation of partitions In the method for forming partition walls using the photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention, the specific methods for supplying the photosensitive resin composition to a substrate, drying, exposing, developing, additional exposure, and heat curing treatment can be the same as those used in the formation of the black matrix described above.

[0250] When used as a partition wall, the size and shape are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the height of the partition wall formed from the photosensitive resin composition is usually about 0.5 to 10 μm.

[0251] [Organic electroluminescent device] The organic electroluminescent device of the present invention comprises a cured product, such as a partition wall, obtained by the production method of the present invention. For example, various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above-described method. Although the method for forming the organic electroluminescent device is not particularly limited, the organic electroluminescent device is preferably manufactured by forming a partition wall pattern on a substrate by the above-described method, and then forming organic layers such as pixels by a vapor deposition method in which a functional material is sublimated in a vacuum and deposited in the area surrounded by the partition walls on the substrate to form a film, or by a wet process such as a casting method, a spin coating method, or an inkjet printing method.

[0252] The types of organic electroluminescent devices include bottom emission types and top emission types. A bottom-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a transparent electrode is laminated, and then laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the partition wall, whereas a top-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a metal electrode layer is laminated, and then laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition wall. Examples of the light-emitting layer include organic electroluminescent layers such as those described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0253] The layer structure is not limited to this, and for example, each of the hole transport layer and the electron transport layer may have a laminate structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0254] The organic electroluminescent element may be formed with each RGB color separated for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent element may have a sealing layer to improve reliability. The sealing layer has the function of preventing moisture in the air from being adsorbed onto the organic electroluminescent element and reducing luminous efficiency. The organic electroluminescent element may have a low-reflection film at the interface with air to improve light extraction efficiency. By disposing the low-reflection film at the interface between air and the element, it is expected that the refractive index gap will be reduced and reflection at the interface will be suppressed. For example, moth-eye structure and super multilayer film technology can be applied to such a low-reflection film.

[0255] When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from the light-emitting layer of a pixel from leaking to other pixels. Furthermore, when electrodes or the like are made of metal, it is necessary to prevent deterioration in image quality due to reflection of external light. Therefore, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent element. In an organic electroluminescent device, since it is necessary to provide electrodes on the upper and lower surfaces of the partition walls, the partition walls preferably have high resistance and low dielectric constant from the viewpoint of insulating properties. Therefore, when a colorant is used to provide the partition walls with light-shielding properties, it is preferable to use the above-mentioned organic pigment having high resistance and low dielectric constant.

[0256] [Image display device] The method for producing an image display device of the present invention is characterized by using a cured product obtained by the production method of the present invention or a black matrix obtained by the production method of the present invention. The image display device of the present invention includes a cured product obtained by the production method of the present invention or a black matrix obtained by the production method of the present invention. The image display device of the present invention has a cured product obtained by curing the photosensitive resin composition of the present invention, and examples of the production method include a production method using the photosensitive resin composition obtained by the production method of the present invention or a cured product, black matrix, or partition wall formed from the photosensitive resin composition of the present invention. The image display device in the present invention is not particularly limited as long as it is a device that displays images or videos, and examples thereof include a liquid crystal display device and an organic EL display, which will be described later.

[0257] [Liquid crystal display device] The liquid crystal display device of the present invention has the black matrix of the present invention, and is not particularly limited in the order or position of forming the color pixels and the black matrix.

[0258] Liquid crystal display devices are typically manufactured by forming an alignment film on a color filter, dispersing spacers on the alignment film, and then bonding it to an opposing substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell, and the cell is then connected to the opposing electrode. A resin film such as polyimide is suitable for the alignment film. Gravure printing and / or flexographic printing are typically used to form the alignment film, with a thickness of several tens of nanometers. After curing the alignment film by thermal baking, the surface is treated with ultraviolet light or a rubbing cloth to create a surface that allows adjustment of the tilt of the liquid crystal.

[0259] The size of the spacer used corresponds to the gap (gap) with the opposing substrate, and a size of 2 to 8 μm is usually suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. An array substrate is usually used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly suitable.

[0260] The gap between the opposing substrate and the substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding with the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and / or heating, sealing the periphery of the liquid crystal cell. The liquid crystal cell with its periphery sealed is cut into panel units, and then the pressure is reduced in a vacuum chamber. After the liquid crystal injection port is immersed in the liquid crystal, the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction inside the liquid crystal cell is usually 1 x 10 -2 ~1×10 -7 Pa, but preferably 1 × 10 -3 ~1×10 -6 Pa. It is also preferable to heat the liquid crystal cell during the reduced pressure, and the heating temperature is usually 30 to 100°C, more preferably 50 to 90°C. The heating during the reduced pressure is usually maintained for 10 to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed by curing a UV-curable resin at the liquid crystal injection port, thereby completing a liquid crystal display device (panel).

[0261] The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystals, thermotropic liquid crystals, etc. Known thermotropic liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0262] [OLED display] The organic EL display of the present invention is produced using the color filter of the present invention or the organic electroluminescent device of the present invention.

[0263] When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1 , a color filter having a pattern formed from a photosensitive resin composition (i.e., pixels 20 and a resin black matrix (not shown) provided between adjacent pixels 20) is first produced on a transparent support substrate 10. An organic protective layer 30 and an inorganic oxide film 40 are then interposed between the color filter and an organic light-emitting element 500 to produce an organic EL element 100. Note that at least one of the pixels 20 and the resin black matrix is ​​produced using the photosensitive resin composition of the present invention. Examples of methods for laminating the organic light-emitting element 500 include sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the top surface of the color filter, and bonding the organic light-emitting element 500 formed on a separate substrate to the inorganic oxide film 40. Using the organic EL element 100 thus produced, an organic EL display can be produced by, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Light Emitting, by Shizuo Tokito, Chinaya Adachi, and Hideyuki Murata).

[0264] The color filter of the present invention can be applied to both passively driven organic EL displays and actively driven organic EL displays.

[0265] [Method for controlling the molecular weight of carboxyl group-containing resin] The method for controlling the molecular weight of a carboxyl group-containing resin of the present invention includes controlling the water content of a first reaction product A-containing liquid obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a second reaction product A-containing liquid, and adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid and reacting them to obtain a carboxyl group-containing resin. The details are the same as those in steps B and C in the method for producing a carboxyl group-containing resin of the present invention.

[0266] When obtaining the carboxyl group-containing resin, the polybasic acid dianhydride (c), the polybasic acid monoanhydride (d), and the polyhydric alcohol (e) may be added to the second reaction product A-containing liquid and reacted to obtain the resin. The preferred types and preferred blending amounts of the epoxy compound (a), the unsaturated monobasic acid (b), the polybasic acid dianhydride (c), the polybasic acid monoanhydride (d), and the polyhydric alcohol (e) are the same as the types and blending amounts described above in the method for producing a carboxy group-containing resin. As the organic solvent used in the reaction for obtaining the first reaction product A-containing liquid, the organic solvents used in the method for producing the carboxy group-containing resin of the present invention can be preferably used. [Example]

[0267] The present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0268] <Examples 1 to 4: Synthesis of carboxyl group-containing resins (1) to (4)>

[0269] [ka]

[0270] 265 g of the epoxy compound (epoxy equivalent weight 240) of the above structure, 80 g of acrylic acid, 350 g of propylene glycol monomethyl ether acetate (PGMEA), 4 g of triphenylphosphine, and 0.3 g of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted with stirring at 100°C until the acid value reached 5 mgKOH / g or less. The reaction took 9 hours, and a first reaction product A-containing liquid containing an intermediate was obtained. After the obtained first reaction product A-containing liquid was cooled to 50°C, the moisture content was measured using a Karl Fischer moisture meter (MKA-610, manufactured by Kyoto Electronics Manufacturing Co., Ltd.), and water was added to the first reaction product A-containing liquid at 50°C while stirring to control the moisture content of the reaction product A-containing liquid to the moisture content shown in Table 1. To the second reaction product A-containing liquid having the controlled water content, 10 g of trimethylolpropane (TMP), 112 g of biphenyltetracarboxylic dianhydride (BPDA), 105 g of tetrahydrophthalic anhydride (THPA), and 374 g of PGMEA were added to a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was reacted at 105°C for 20 hours with stirring to obtain carboxyl group-containing resin-containing liquids containing carboxyl group-containing resins (1) to (4), respectively. The weight average molecular weights (Mw) of the resulting carboxyl group-containing resins (1) to (4) in terms of polystyrene were measured by GPC (Waters, 2695).

[0271] [Table 1]

[0272] Examples 1 to 4 shown in Table 1 show that the weight average molecular weight of the carboxy group-containing resin can be controlled by including a step of controlling the moisture content of the reaction product A-containing liquid. As described above, according to the production method of the present invention, it is possible to control the molecular weight of the carboxyl group-containing resin, and it is possible to maintain the performance stability of the carboxyl group-containing resin between production lots.

Claims

1. a step A of reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a liquid containing a first reaction product A; A step B of controlling the water content of the first reaction product A-containing liquid to obtain a second reaction product A-containing liquid; and a step C of adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid and reacting them to obtain a carboxy group-containing resin, In the step B, water is added to the first reaction product A-containing liquid to control the moisture content of the first reaction product A-containing liquid, thereby obtaining the second reaction product A-containing liquid; In the step C, the amount of the polybasic acid dianhydride (c) used is 0.5 equivalents or more and 50 equivalents or less relative to 1 equivalent of the polybasic acid monoanhydride (d).

2. 2. The method for producing a carboxyl group-containing resin according to claim 1, wherein water is added to the first reaction product A-containing liquid so that the moisture content of the second reaction product A-containing liquid is 0.1 mass % or more and 0.5 mass % or less.

3. The method for producing a carboxyl group-containing resin according to claim 1 or 2, wherein in step C, a polyhydric alcohol (e) is further added and reacted.

4. The method for producing a carboxyl group-containing resin according to claim 3 , wherein the polyhydric alcohol (e) includes trimethylolpropane.

5. The method for producing a carboxy group-containing resin according to any one of claims 1 to 4, wherein the polybasic acid dianhydride (c) includes biphenyltetracarboxylic dianhydride.

6. The method for producing a carboxy group-containing resin according to any one of claims 1 to 5, wherein the polybasic acid monoanhydride (d) includes tetrahydrophthalic anhydride.

7. A method for producing an ink containing (A) an alkali-soluble resin, an organic solvent, and (D) a colorant, the method comprising the steps of: A method for producing an ink, comprising blending a carboxy group-containing resin produced by the method according to any one of claims 1 to 6 as the alkali-soluble resin (A).

8. A method for producing a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, the method comprising: A method for producing a photosensitive resin composition, comprising blending, as the alkali-soluble resin (A), a carboxy group-containing resin produced by the production method according to any one of claims 1 to 6.

9. The method for producing a photosensitive resin composition according to claim 8 , wherein the photosensitive resin composition further contains (D) a colorant.

10. A method for producing a cured product, comprising curing a photosensitive resin composition obtained by the method according to claim 8 or 9.

11. A method for producing a black matrix, comprising forming a black matrix using the cured product obtained by the method for producing a black matrix according to claim 10.

12. A method for producing an image display device, comprising using a cured product obtained by the method according to claim 10 or a black matrix obtained by the method according to claim 11.

13. A method for controlling the molecular weight of a carboxy group-containing resin, comprising: controlling the water content of a first reaction product A-containing liquid obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a second reaction product A-containing liquid; and adding a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid and reacting them to obtain a carboxy group-containing resin.

14. 14. The method for controlling the molecular weight of a carboxy group-containing resin according to claim 13, wherein the second reaction product A-containing liquid is obtained by adding water to the first reaction product A-containing liquid to control the moisture content of the first reaction product A-containing liquid so that the moisture content of the solution containing the second reaction product A-containing liquid is 0.1 mass % or more and 0.5 mass % or less.

15. 15. The method for controlling the molecular weight of a carboxyl group-containing resin according to claim 13 or 14, wherein the carboxyl group-containing resin is a carboxyl group-containing resin obtained by adding a polybasic acid dianhydride (c), a polybasic acid monoanhydride (d), and a polyhydric alcohol (e) to the second reaction product A-containing liquid and allowing the mixture to react.

16. The method for controlling the molecular weight of a carboxy group-containing resin according to claim 15, wherein the polyhydric alcohol (e) includes trimethylolpropane.

17. The method for controlling the molecular weight of a carboxy group-containing resin according to any one of claims 13 to 16, wherein the polybasic acid dianhydride (c) comprises biphenyltetracarboxylic dianhydride.

18. The method for controlling the molecular weight of a carboxy group-containing resin according to any one of claims 13 to 17, wherein the polybasic acid monoanhydride (d) includes tetrahydrophthalic anhydride.

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