Methods for manufacturing resins containing carboxyl groups, methods for manufacturing inks, methods for manufacturing photosensitive resin compositions, methods for manufacturing cured materials, methods for manufacturing black matrices, methods for manufacturing image display devices, and methods for controlling the molecular weight of resins containing carboxyl groups.

Abstract

This invention provides a method for manufacturing a carboxyl-containing resin with controllable molecular weight and excellent batch-to-batch performance stability, as well as a method for controlling the molecular weight of the carboxyl-containing resin. The method for manufacturing the carboxyl-containing resin of this invention comprises the following steps: Step A, 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, controlling the water content of the first reaction product A containing liquid to obtain a second reaction product A containing liquid; and Step C, adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second reaction product A containing liquid and reacting them to obtain a carboxyl-containing resin.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a resin containing carboxyl groups, a method for manufacturing ink, a method for manufacturing a photosensitive resin composition, a method for manufacturing a cured material, a method for manufacturing a black matrix, a method for manufacturing an image display device, and a method for controlling the molecular weight of a resin containing carboxyl groups. This case asserts priority based on Japan’s Special Application No. 2020-182984 filed on October 30, 2020, the contents of which are incorporated herein by reference. Prior Technology

[0002] Color filters are typically formed by creating a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors, such as red, green, and blue, in patterns such as grids, stripes, or mosaics. The pattern size varies depending on the application of the color filter and the colors, and is usually around 5 to 700 μm.

[0003] As a representative manufacturing method for color filters, photolithography using photosensitive resin compositions is currently known. In the case of manufacturing color filters by photolithography, a photosensitive resin composition containing carboxyl-containing resins that can be alkaline-developed is first coated onto a transparent substrate and then dried. Next, an image is exposed, developed using an alkaline developer, and then hardened (cured) by high-temperature treatment at 200°C or higher, thereby forming a pattern. However, for this type of photosensitive resin composition, the linewidth or film thickness varies depending on the molecular weight of the carboxyl-containing resin, resulting in significant differences in molecular weight between batches of the carboxyl-containing resin and a decrease in the yield of color filters.

[0004] Against this backdrop, there is a need for a method to stably manufacture resins containing carboxyl groups by controlling their molecular weight. For example, Patent Documents 1 and 2 describe methods for manufacturing resins containing carboxyl groups using specific conditions. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2000-336116 [Patent Document 2] Japanese Patent Application Publication No. 2005-41958 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] When the inventors manufactured a resin containing carboxyl groups using the manufacturing method described in Patent Documents 1-2, they found that the molecular weight stability between manufacturing batches was insufficient.

[0008] Therefore, the object of the present invention is to provide a method for manufacturing a carboxyl-containing resin with controllable molecular weight and excellent batch-to-batch performance stability, and a method for controlling the molecular weight of the carboxyl-containing resin. [Technical means to solve the problem]

[0009] The inventors conducted in-depth research to solve the aforementioned problems and discovered that by using a specific method to manufacture a resin containing carboxyl groups, the aforementioned problems can be solved. That is, the main points of this invention are as follows.

[0010] [1] A method for manufacturing a resin containing carboxyl groups, comprising the following steps: Step A, namely, reacting the epoxy compound (a) with the unsaturated monobasic acid (b) in an organic solvent to obtain the first reaction product A containing liquid; Step B, namely, controlling the water content of the liquid containing the first reaction product A to obtain the liquid containing the second reaction product A; and Step C involves adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the liquid containing the second reaction product A and reacting them to obtain a resin containing carboxyl groups. [2] As in [1], the method for manufacturing a resin containing a carboxyl group, wherein water is added to the liquid containing the first reaction product A to control the water content of the liquid containing the first reaction product A, thereby obtaining the liquid containing the second reaction product A. [3] In the method for manufacturing a resin containing a carboxyl group as described in [2], water is added to the liquid containing the first reaction product A in such a way that the water content of the liquid containing the second reaction product A is 0.1% by mass or more and 0.5% by mass or less. [4] A method for manufacturing a carboxyl-containing resin as described in any of [1] to [3], wherein in step C above, a polyol (e) is added and reacted. [5] The method for manufacturing a resin containing a carboxyl group as described in [4], wherein the polyol (e) contains trimethylolpropane. [6] A method for manufacturing a carboxyl-containing resin as described in any of [1] to [5], wherein the aforementioned polybasic acid dianhydride (c) comprises biphenyltetracarboxylic acid dianhydride. [7] A method for manufacturing a carboxyl-containing resin as described in any of [1] to [6], wherein the aforementioned polybasic acid monohydric anhydride (d) comprises tetrahydrophthalic anhydride. [8] A method for manufacturing an ink, comprising (A) an alkali-soluble resin, an organic solvent, and (D) a pigment, and It includes: a carboxyl-containing resin manufactured by any one of the manufacturing methods of [1] to [7] as the above-mentioned (A) alkali-soluble resin. [9] A method for manufacturing a photosensitive resin composition, comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and It includes: a carboxyl-containing resin manufactured by any one of the manufacturing methods of [1] to [7] as the above-mentioned (A) alkali-soluble resin.

[10] A method for manufacturing a photosensitive resin composition as described in [9], wherein the photosensitive resin composition further contains (D) a colorant.

[11] A method for manufacturing a hardened material, comprising: hardening a photosensitive resin composition obtained by a manufacturing method such as [9] or

[10] .

[12] A method for manufacturing a black matrix, comprising: forming a black matrix using a hardened material obtained by the manufacturing method of

[11] .

[13] A method for manufacturing an image display device, characterized in that: it uses a hardened material obtained by the manufacturing method of

[11] or a black matrix obtained by the manufacturing method of

[12] .

[14] A method for controlling the molecular weight of a resin containing carboxyl groups, 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, thereby obtaining a second reaction product A containing liquid; adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second reaction product A containing liquid and reacting them, thereby obtaining a resin containing carboxyl groups.

[15] The method for controlling the molecular weight of a carboxyl-containing resin as described in

[14] involves adding water to the solution containing the second reaction product A to control the water content of the first reaction product A, thereby obtaining the second reaction product A.

[16] The method for controlling the molecular weight of a carboxyl-containing resin as described in

[14] or

[15] , wherein the carboxyl-containing resin is obtained by adding a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) to the liquid containing the second reaction product A and reacting them.

[17] The method for controlling the molecular weight of a carboxyl-containing resin as in

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

[18] A method for controlling the molecular weight of a carboxyl-containing resin as described in any of

[14] to

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

[19] A method for controlling the molecular weight of a carboxyl-containing resin as described in any of

[14] to

[18] , wherein the aforementioned polybasic acid monohydric anhydride (d) comprises tetrahydrophthalic anhydride. [Effects of the Invention]

[0011] According to the present invention, a method for manufacturing a carboxyl-containing resin with controllable molecular weight and excellent batch-to-batch performance stability is provided, as well as a method for controlling the molecular weight of the carboxyl-containing resin. Simple Explanation of the Diagram

[0012] Figure 1 is a schematic cross-sectional view of an example of an organic EL (Electroluminescence) element incorporating the color filter of the present invention. Implementation

[0013] The following describes specific 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 its spirit. Furthermore, in this invention, "(meth)acrylic acid" refers to "acrylic acid and / or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acrylic acid".

[0014] In this invention, "all solid components" refers to all components other than organic solvents and water contained in the photosensitive resin composition or the ink described below. In this invention, the "photosensitive resin composition" is sometimes referred to as "photoresist". In this invention, the so-called weight average molecular weight refers to the weight average molecular weight (Mw) of polystyrene determined by gel permeation chromatography (GPC). In this invention, the term "amine value," unless otherwise specified, refers to the amine value converted from the effective solid content, which is expressed as the mass of KOH equivalent to the amount of alkali in 1 g of the dispersant's solid content. Furthermore, the determination method is described below.

[0015] [Manufacturing method of resins containing carboxyl groups] The method for manufacturing a carboxyl-containing resin of the present invention comprises the following steps: Step A, that is, 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, that is, 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, that is, adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second reaction product A containing liquid obtained in Step B and reacting them to obtain a carboxyl-containing resin. The first reaction product A obtained in step A, which contains reaction product A in the liquid, can also be called an intermediate of a resin containing a carboxyl group, and is therefore sometimes referred to as an "intermediate" below. Similarly, the second reaction product A obtained in step B, which contains reaction product A in the liquid, is also sometimes referred to as an "intermediate". The liquid containing the first reaction product A and the liquid containing the second reaction product A can be a suspension, dispersion or solution, provided that it is a liquid mixture containing the reaction product A, and is preferably a solution containing the reaction product A.

[0016] <Step A> Step A is as follows: reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to synthesize reaction product A (intermediate), thereby obtaining a first reaction product A containing liquid.

[0017] As for the epoxy compound (a), there are no particular limitations as long as it is a compound containing epoxy groups. For example, the following are preferred: bisphenol A type epoxy resins (e.g., "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), and bisphenol F type resins (e.g., Mitsubishi... Epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "jER807", "EP-4001", "EP-4002", "EP-4004, etc."), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical Co., Ltd.'s "YX-4000"), phenolic varnish type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-201", Mitsubishi Chemical Co., Ltd.'s "EP-152", "EP-154", etc.), Dow Chemical Company's "DEN-438", (ortho, meta, para-)cresol phenolic varnish epoxy resins (e.g., Nippon Kayaku Co.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanate (e.g., Nissan Chemical Co.'s "TEPIC"), triphenol methane epoxy resins (e.g., Nippon Kayaku Co.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resins (Daicel Company's "Celloxide 2021P", "Celloxide..."). EHPE), epoxy resins obtained by glycidizing phenolic resins generated by the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), copolymers of (meth)acrylates containing epoxy groups and other free radical polymerizable monomers, and epoxy compounds represented by the following general formulas (a1) to (a6). Specifically, for example, as an epoxy compound represented by the following general formula (a1), "XD-1000" manufactured by Nippon Chemical Co., Ltd. can be cited as an example; as an epoxy compound represented by the following general formula (a2), "NC-3000" manufactured by Nippon Chemical Co., Ltd. can be cited as an example; and as an epoxy compound represented by the following general formula (a4), "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. can be cited as an example.

[0018] [Chemistry 1]

[0019] In the above general formula (a1), b11 represents the average value, which is a number from 0 to 10. R11 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the multiple R11s present in a molecule may be the same or different from each other.

[0020] [Chemistry 2]

[0021] In the above general formula (a2), b12 represents the average value, which is a number from 0 to 10. R21 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the multiple R21s present in a molecule may be the same or different from each other.

[0022] [Chemistry 3]

[0023] In the above general formula (a3), X represents the linking group represented by the following general formula (a3-1) or (a3-2). The molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0024] Of these, from the viewpoint of photoresist pattern forming characteristics, X is preferably (a3-1) and b13 is preferably 2.

[0025] [Chemistry 4]

[0026] In the above general formulas (a3-1) and (a3-2), R 31~R 34 and R 35~R 37 each independently represent an adamantyl alkyl group that may have substituents, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, or a phenyl group that may have substituents. Furthermore, * in the formula represents a bonding site in formula (a3).

[0027] From the viewpoint of photoresist pattern forming characteristics, formula (a3-1) preferably has two adamantyl alkyl groups and two hydrogen atoms. From the viewpoint of photoresist pattern forming characteristics, formula (a3-2) preferably has two adamantyl alkyl groups and one hydrogen atom.

[0028] [Chemistry 5]

[0029] In the above general formula (a4), p and q each independently represent integers from 0 to 4, R 41 and R 42 each independently represent alkyl or halogen atoms having 1 to 20 carbon atoms, R 43 and R 44 each independently represent alkyl groups having 1 to 5 carbon atoms, and x and y each independently represent integers greater than 0.

[0030] Of these, from the viewpoint of photoresist pattern forming characteristics, p, q, x, and y are preferably 0.

[0031] [Chemistry 6]

[0032] In the above general formula (a5), R51 to R54 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms; R55 is an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms; and R56 is each independently an alkyl group with 1 to 5 carbon atoms. k is an integer from 1 to 5, l is an integer from 0 to 13, and m is an independent integer from 0 to 5.

[0033] Of these, from the viewpoint of photoresist pattern forming characteristics, R 51 to R 54 are preferably hydrogen atoms, k is preferably 2, and l and m are preferably 0.

[0034] [Chemistry 7]

[0035] In the above general formula (a6), n and o are independent integers from 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. Furthermore, multiple R 23s present in a molecule may be the same or different from each other.

[0036] Of these, from the viewpoint of photoresist pattern forming characteristics, it is preferable to use an epoxy compound represented by any of the 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).

[0037] An unsaturated monocarboxylic acid (b) is any compound having only one acid group and one or more free radical polymerizable unsaturated bonds in one molecule, and the acid group is preferably a carboxyl group. By reacting an epoxy compound (a) with an 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 an intermediate with a free radical polymerizable double bond introduced into the epoxy compound.

[0038] Examples of unsaturated monocarboxylic acids (b) include: (meth)acrylic acid, butenoic acid, ortho-, meta-, and para-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substitutions at the α-position of (meth)acrylic acid, 2-(meth)propenyloxyethyl succinic acid, 2-(meth)propenyloxyethyl adipic acid, 2-(meth)propenyloxyethyl phthalic acid, 2-(meth)propenyloxyethyl hexahydrophthalic acid, 2-(meth)propenyloxyethyl maleic acid, 2-(meth)propenyloxypropyl succinic acid, 2-(meth)propenyloxypropyl adipic acid, 2-(meth)propenyloxypropyl tetrahydrophthalic acid, 2-(meth)propenyloxypropyl phthalic acid, 2-(meth)propenyloxypropyl maleic acid, 2-(meth)propenyloxypropyl maleic acid, etc. Acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, monomers having a carboxyl group at the end formed by adding ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerol to (meth)acrylic acid, monomers having a hydroxyl group at the end formed by adding succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride), etc. to compounds ...

[0039] From the viewpoint of light resistance sensitivity and stability over time, alkenyl carboxylic acid is preferred as an unsaturated monocarboxylic acid (b), and (meth)acrylic acid is even more preferred.

[0040] As organic solvents, for example, 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 can be used. 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.

[0041] As a method for reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent to obtain an intermediate, a known method can be used. For example, the epoxy compound (a) can be reacted with the unsaturated monocarboxylic acid (b) in an organic solvent in the presence of a catalyst and a polymerization inhibitor at a temperature of 50 to 150°C.

[0042] As a catalyst, for example, tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and diethylbenzylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used. Among these, tertiary phosphine is preferred from the viewpoint of reaction yield, and triphenylphosphine is more preferred.

[0043] As polymerization inhibitors, for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, p-methoxyphenol, and 2,6-di-tert-butyl-4-cresol can be used. Among these, from the viewpoint of reaction yield and photosensitivity, p-methoxyphenol and 2,6-di-tert-butyl-4-cresol are preferred, and p-methoxyphenol is even more preferred.

[0044] Furthermore, epoxy compounds (a), unsaturated monocarboxylic acids (b), organic solvents, catalysts, and polymerization inhibitors can be used individually or in combination with two or more.

[0045] The amount of unsaturated monocarboxylic acid (b) used relative to the epoxy group of epoxy compound (a) is preferably in the range of 0.5 to 1.5 equivalents, and more preferably in the range of 0.8 to 1.2 equivalents. By using the amount of unsaturated monocarboxylic acid (b) at or above the aforementioned lower limit, the amount of residual epoxy is reduced, which can suppress the tendency for gelation during the reaction with the polycarboxylic anhydride in step B. Furthermore, by using the amount at or below the aforementioned upper limit, the tendency for unsaturated monocarboxylic acid (b) to remain as unreacted material can be suppressed.

[0046] <Step B> Step B is to control the water content of the liquid containing the first reaction product A obtained in step A, thereby obtaining the liquid containing the second reaction product A. By including step B in the manufacturing method of the carboxyl-containing resin of the present invention, the molecular weight of the carboxyl-containing resin can be controlled.

[0047] There are no particular limitations on the method for controlling the water content of the liquid containing the first reaction product A obtained in step A. For example, the method of adding water to the liquid containing the first reaction product A and the method of dehydrating the liquid containing the first reaction product A can be cited.

[0048] When water is added to the liquid containing the first reaction product A, water can be added alone or as a mixture of water and an organic solvent. Furthermore, the temperature of the liquid containing the first reaction product A during addition is preferably 20°C to 80°C, more preferably 30°C to 70°C, further preferably 40°C to 60°C, and even more preferably 45°C to 55°C. By setting the temperature within the above range, water can be uniformly dispersed and dissolved in the liquid containing the first reaction product A. The addition of water to the liquid containing the first reaction product A is preferably carried out while stirring the liquid containing the first reaction product A. This allows the water to be uniformly dispersed and dissolved in the liquid containing the first reaction product A.

[0049] The amount of water added to the liquid containing the first reaction product A is preferably added such that the water content of the liquid containing the second reaction product A obtained in step B is 0.01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.06% by mass or more, further preferably 0.1% by mass or more, and especially preferably 0.18% by mass or more. It is also preferably 1% by mass or less, more preferably 0.8% by mass or less, further preferably 0.6% by mass or less, further preferably 0.5% by mass or less, and especially preferably 0.4% by mass or less. By setting the amount to the lower limit or above, there is a tendency to reduce the residue of the photoresist. Furthermore, by setting the amount to the upper limit or below, there is a tendency to improve the time-dependent stability of the photoresist. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01~1% by mass, more preferably 0.03~0.8% by mass, further preferably 0.06~0.6% by mass, further preferably 0.1~0.5% by mass, and even more preferably 0.18~0.4% by mass.

[0050] Methods for dehydrating the liquid containing the first reaction product A include: drying it using porous materials such as molecular sieves or silicone, or dehydrating agents such as calcium chloride; or removing it by reducing pressure and distillation. Of these methods, from the viewpoint of the purity or yield of the resin containing carboxyl groups, the method of removing it by reducing pressure and distillation is preferred. When removing the product by depressurization and distillation, it is preferable to set the pressure inside the reaction vessel containing the liquid containing the first reaction product A to 70 kPa or less, more preferably 60 kPa or less, even more preferably 50 kPa or less, and especially preferably 40 kPa or less.

[0051] In step B, from the viewpoint of reaction time, it is preferable to have the following steps: by adding water to the liquid containing the first reaction product A obtained in step A, the water content of the liquid containing the first reaction product A is controlled, thereby obtaining the liquid containing the second reaction product A.

[0052] The water content of the reaction product A containing liquid can be calculated using the Karl Fischer method described in JIS K0113 (2005). Various moisture meters can be used, such as the MKA-610 manufactured by Kyoto Electronics Co., Ltd.

[0053] <Step C> Step C involves adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the liquid of the second reaction product A obtained in step B and reacting them to obtain a resin containing carboxyl groups.

[0054] As a polybasic acid dianhydride (c), any compound having only two anhydride groups in one molecule is acceptable. From the viewpoint of photoresist patterning properties, compounds containing the general formula (c1) are preferred.

[0055] [Chemistry 8]

[0056] In the above formula (c1), A is derived from the tetravalent organic group of the dianhydride of a polybasic acid.

[0057] For example, the polybasic acid dianhydride (c) represented by the general formula (c1) can be: biphenyltetracarboxylic dianhydride (BPDA), dicyclohexyltetracarboxylic dianhydride, pyromellitic tetracarboxylic anhydride, and benzophenone tetracarboxylic dianhydride. Among these, from the viewpoint of photoresist patterning characteristics, biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic tetracarboxylic anhydride are preferred, and biphenyltetracarboxylic dianhydride (BPDA) is even more preferred.

[0058] As a polybasic acid monohydric anhydride (d), any compound having only one anhydride group in one molecule is acceptable. Examples include: maleic anhydride, succinic anhydride, itanic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl terephthalic anhydride, terephthalic anhydride, and trimellitic anhydride. Among these, from the viewpoint of photoresist patterning properties, succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are preferred, and tetrahydrophthalic anhydride is even more preferred.

[0059] Both polybasic acid dianhydrides (c) and polybasic acid monohydrides (d) can be used alone or in combination with more than one.

[0060] The reaction of adding polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) to the liquid containing the second reaction product A and reacting them to synthesize a resin containing a carboxyl group can also be carried out by known methods. For example, polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) can be added to the liquid containing the second reaction product A and reacted at a temperature of 50 to 150°C.

[0061] When a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) are added to the liquid containing the second reaction product A, a polyol (e) can be added and reacted. By adding polyol (e) and reacting it, a multi-branched structure can be introduced into the obtained carboxyl-containing resin, thereby improving the photoresist patterning properties.

[0062] As a polyol (e), for example, trimethylolpropane, pentaerythritol, and dipentaerythritol can be used. Among these, trimethylolpropane is preferred from the viewpoint of photoresist patterning characteristics.

[0063] The amount of polyol (e) used relative to 1 equivalent of the unsaturated monocarboxylic acid (b) is preferably 0.01 equivalents or more, more preferably 0.03 equivalents or more, and even more preferably 0.05 equivalents or more. It is also 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 above, there is a tendency to improve the time-dependent stability of the photoresist; and by setting it to the upper limit or below, there is a tendency to improve the photoresist sensitivity. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 1 equivalent, more preferably 0.03 to 0.9 equivalent, and even more preferably 0.05 to 0.8 equivalent.

[0064] The amount of dianhydride (c) used relative to 1 equivalent of the monohydric anhydride (d) is preferably 0.1 equivalents or more, more preferably 0.3 equivalents or more, and even more preferably 0.5 equivalents or more. Furthermore, 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 above, there is a tendency to improve the adhesion of the photoresist; and by setting it to the upper limit or below, there is a tendency to reduce the residue of the photoresist. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 50 equivalent, more preferably 0.3 to 30 equivalent, and even more preferably 0.5 to 10 equivalent.

[0065] The acid value of the carboxyl-containing resin manufactured using the method of the present invention is preferably 10 mgKOH / g or higher, more preferably 30 mgKOH / g or higher, even more preferably 50 mgKOH / g or higher, and particularly preferably 80 mgKOH / g or higher. It is also preferably 250 mgKOH / g or lower, more preferably 200 mgKOH / g or lower, even more preferably 150 mgKOH / g or lower, and particularly preferably 130 mgKOH / g or lower. By setting the acid value to the lower limit or higher, there is a tendency to reduce the residue of the photoresist. Furthermore, by setting the acid value to the upper limit or lower, there is a tendency to improve the adhesion of the photoresist. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10~250 mgKOH / g, more preferably 30~200 mgKOH / g, further preferably 50~150 mgKOH / g, and even more preferably 80~130 mgKOH / g.

[0066] The weight-average molecular weight of the carboxyl-containing resin manufactured using the manufacturing method of the present invention is preferably 3000 or more, more preferably 5000 or more, further preferably 8000 or more, and even more preferably 12000 or more. It is also preferably 22000 or less, and more preferably 21000 or less. By setting the value to the lower limit or above, there is a tendency to improve the adhesion of the photoresist. Furthermore, by setting the value to the upper limit or below, there is a tendency to reduce the residue of the photoresist. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 3000~22000, more preferably 5000~22000, further preferably 8000~21000, and even more preferably 12000~21000.

[0067] [Resin containing carboxyl groups] The resin-containing liquid containing the carboxyl-containing resin obtained in step C comprises the carboxyl-containing resin, an organic solvent, and water. The water content of the obtained carboxyl-containing resin-containing liquid is preferably 0.01% by mass or more and 1% by mass or less. By keeping the water content within the above range, there is a tendency to reduce the residue of photoresist containing carboxyl-containing resins and to improve the long-term stability of the photoresist. The water content of the resin solution containing carboxyl groups is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more, further preferably 0.06% by mass or more, further preferably 0.1% by mass or more, and especially preferably 0.18% by mass or more. More preferably, it is 0.8% by mass or less, further preferably 0.6% by mass or less, further preferably 0.5% by mass or less, and especially 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, further preferably 0.1% by mass or more and 0.5% by mass or less, and especially preferably 0.18% by mass or more and 0.4% by mass or less. By setting the water content to the above lower limit or above, there is a tendency to reduce the residue of the photoresist containing the above resin solution. Furthermore, by setting it below the aforementioned upper limit, there is a tendency for the time-dependent stability of the photoresist to improve.

[0068] The carboxyl-containing resin contained in the liquid of the present invention is preferably a carboxyl-containing resin manufactured using the manufacturing method of the present invention. The carboxyl-containing resin of the present invention preferably has a structure derived from an epoxy compound (a). The carboxyl-containing resin of the present invention preferably has a structure derived from an unsaturated monobasic acid (b). The carboxyl-containing resin of the present invention preferably has a structure derived from the dianhydride (c) of a polybasic acid. The carboxyl-containing resin of the present invention preferably has a structure derived from monohydric anhydride (d) of a polybasic acid. The carboxyl-containing resin of the present invention preferably has a structure derived from polyol (e). The preferred types or preferred amounts of epoxy compounds (a), unsaturated monocarboxylic acids (b), polycarboxylic acid dianhydrides (c), polycarboxylic acid monohydrides (d), and polyols (e) are the same as those mentioned above.

[0069] As the organic solvent contained in the resin containing carboxyl groups, the organic solvent used in the method for manufacturing the resin containing carboxyl groups of the present invention can be preferred.

[0070] [Photosensitive Resin Composition] The method for manufacturing the photosensitive resin composition of the present invention comprises a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and further comprises: adjusting a carboxyl-containing resin manufactured using the method of the present invention as (A) the alkali-soluble resin. Furthermore, the photosensitive resin composition manufactured using the method of the present invention may contain (D) a pigment.

[0071] <(A) Alkali-soluble resin> By including a carboxyl-containing resin obtained by the manufacturing method of the present invention as an (A) alkali-soluble resin in the photosensitive resin composition of the present invention, the performance stability between manufacturing batches can be improved. (A) Alkali-soluble resins may contain other alkali-soluble resins.

[0072] As for other alkali-soluble resins, there is no particular limitation as long as the solubility of the exposed and unexposed areas to alkali development changes after exposure of the coating obtained by coating a photosensitive resin composition and drying it. Alkali-soluble resins containing carboxyl groups are preferred. Furthermore, resins containing vinyl unsaturated groups are preferred, and even more preferred are alkali-soluble resins containing both vinyl unsaturated groups and carboxyl groups. Specific examples include epoxy (meth)acrylate resins or acrylic copolymer resins containing carboxyl groups. Specific examples include alkali-soluble resins described below as (A1-1), (A2-1), (A2-2), (A2-3), and (A2-4). One or more of these can be used. Among the above, epoxy (meth)acrylate resins containing carboxyl groups (A1-1) are particularly preferred.

[0073] In the manufacture of color filters, to ensure the non-exposed portions dissolve in alkaline developing solutions, polymeric resins with acidic functional groups such as hydroxyl, carboxyl, phosphate, and sulfonic acid groups are used as the polymeric resin. Among these, from the viewpoint of solubility in alkaline developing solutions, polymeric resins with carboxyl groups are preferred. However, while phosphate or sulfonic acid groups are more acidic than carboxyl groups, they readily react with initiators, monomers, dispersants, and other additives with basic groups in the photosensitive resin composition, potentially leading to decreased storage stability.

[0074] Examples of epoxy (meth)acrylate resins having carboxyl groups include the following epoxy (meth)acrylate resin (A1-1).

[0075] <Epoxy (meth)acrylate resin (A1-1)> An alkali-soluble resin is obtained by adding an unsaturated monocarboxylic acid to an epoxy compound and then reacting it with a monohydric anhydride of a polycarboxylic acid.

[0076] <Epoxy (meth)acrylate resin with carboxyl and vinyl unsaturated bonds (A1-1)> Epoxy compounds that can be used as raw materials include, for example, bisphenol A type epoxy resins (such as "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (such as "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), and bisphenol F type resins (such as Mitsubishi... Epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "jER807", "EP-4001", "EP-4002", "EP-4004, etc."), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical Co., Ltd.'s "YX-4000"), phenolic varnish type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-201", Mitsubishi Chemical Co., Ltd.'s "EP-152", "EP-154", etc.), Dow Chemical Company's "DEN-438", (ortho, meta, para-)cresol phenolic varnish epoxy resins (e.g., Nippon Kayaku Co.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanate (e.g., Nissan Chemical Co.'s "TEPIC"), triphenol methane epoxy resins (e.g., Nippon Kayaku Co.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resins (Daicel Company's "Celloxide 2021P", "Celloxide..."). EHPE”), epoxy resins obtained by glycidizing phenolic resins generated by the reaction of dicyclopentadiene and phenol (e.g., “EXA-7200” manufactured by DIC Corporation, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (a1) to (a6). Specifically, for example, epoxy resin represented by the following general formula (a1) can be exemplified by "XD-1000" manufactured by Nippon Kayaku Co., Ltd.; epoxy resin represented by the following general formula (a2) can be exemplified by "NC-3000" manufactured by Nippon Kayaku Co., Ltd.; and epoxy resin represented by the following general formula (a4) can be exemplified by "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.

[0077] [Chemistry 9]

[0078] In the above general formula (a1), b11 represents the average value, which is a number from 0 to 10. R11 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the multiple R11s present in a molecule may be the same or different from each other.

[0079] [Chemistry 10]

[0080] In the above general formula (a2), b12 represents the average value, which is a number from 0 to 10. R21 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the multiple R21s present in a molecule may be the same or different from each other.

[0081] [Chemistry 11]

[0082] In the above general formula (a3), X represents the linking group represented by the following general formula (a3-1) or (a3-2). The molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0083] [Chemistry 12]

[0084] In the above general formulas (a3-1) and (a3-2), R 31~R 34 and R 35~R 37 each independently represent an adamantyl alkyl group that may have substituents, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, or a phenyl group that may have substituents. Furthermore, * in the formula represents a bonding site in formula (a3). From the viewpoint of photoresist pattern forming characteristics, formula (a3-1) preferably has two adamantyl alkyl groups and two hydrogen atoms. From the viewpoint of photoresist pattern forming characteristics, formula (a3-2) preferably has two adamantyl alkyl groups and one hydrogen atom.

[0085] [Chemistry 13]

[0086] In the above general formula (a4), p and q each independently represent integers from 0 to 4, R 41 and R 42 each independently represent alkyl or halogen atoms having 1 to 20 carbon atoms, R 43 and R 44 each independently represent alkyl groups having 1 to 5 carbon atoms, and x and y each independently represent integers greater than 0.

[0087] [Chemistry 14]

[0088] In the above general formula (a5), R51 to R54 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms; R55 is an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms; and R56 is each independently an alkyl group with 1 to 5 carbon atoms. k is an integer from 1 to 5, l is an integer from 0 to 13, and m is an independent integer from 0 to 5.

[0089] [Chemistry 15]

[0090] In the above general formula (a6), n and o are independent integers from 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. Furthermore, multiple R 23s present in a molecule may be the same or different from each other.

[0091] Of these, epoxy compounds represented by any one of the general formulas (a1), (a2) or (a6) are preferred.

[0092] Examples of unsaturated monocarboxylic acids include: (meth)acrylic acid, butenoic acid, ortho-, meta-, and p-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substitutions at the α-position of (meth)acrylic acid, 2-(meth)propenyl acetoethyl succinic acid, 2-(meth)propenyl acetoethyl adipic acid, 2-(meth)propenyl acetoethyl phthalic acid, 2-(meth)propenyl acetoethyl hexahydrophthalic acid, 2-(meth)propenyl acetoethyl maleic acid, and 2-(meth)propenyl acetoethyl maleic acid. Acryloxypropylsuccinic acid, 2-(meth)propenyl acryloxypropyl adipic acid, 2-(meth)propenyl acryloxypropyl tetrahydrophthalic acid, 2-(meth)propenyl acryloxypropyl phthalic acid, 2-(meth)propenyl acryloxypropyl maleic acid, 2-(meth)propenyl acryloxybutylsuccinic acid, 2-(meth)propenyl acryloxybutyl adipic acid, 2-(meth)propenyl acryloxybutyl hydrogen phthalic acid, 2-(meth)propenyl acryloxybutyl phthalic acid, 2-(meth)propenyl acryloxybutyl maleic acid, As monomers that have a carboxyl group at the end, and which are lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone added to (meth)acrylic acid, esters are considered to be formed. Alternatively, succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride), or other acids (anhydrides) such as pentaerythritol tri(meth)acrylate with one or more ethylene unsaturated groups and one carboxyl group at the end can be added to monomers such as (meth)acrylate hydroxyalkyl esters with one hydroxyl group at the end, or compounds such as pentaerythritol tri(meth)acrylate with one hydroxyl group at the end, to form (meth)acrylate or (meth)acrylate dimers.

[0093] Of these, (meth)acrylic acid is particularly preferred in terms of sensitivity. As a method for the addition reaction of unsaturated monocarboxylic acids, known methods can be used. For example, the unsaturated monocarboxylic acid can be reacted with an epoxy compound at a temperature of 50 to 150°C in the presence of an esterification catalyst. Examples of catalysts used here include: tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine; tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and diethylbenzylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0094] Furthermore, epoxy compounds, unsaturated monocarboxylic acids, and catalysts can be used individually or in combination with two or more. The amount of unsaturated monocarboxylic acid used relative to the epoxy group of the epoxy compound is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents. By using an amount of unsaturated monocarboxylic acid above the aforementioned lower limit, the amount of unsaturated groups introduced becomes sufficient, the subsequent reaction with the monohydric anhydride of the polybasic acid becomes sufficient, and the tendency for a large amount of epoxy groups to remain is suppressed. On the other hand, by using an amount below the aforementioned upper limit, the tendency for unsaturated monocarboxylic acid to remain as unreacted material is suppressed.

[0095] Examples of monohydric anhydrides derived from polybasic acids include: one or more monohydric anhydrides selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, methylhexahydrophthalic acid, inner methylenetetrahydrophthalic acid, chloramphenic acid, and methyltetrahydrophthalic acid.

[0096] Preferred anhydrides are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. Tetrahydrophthalic acid monoanhydride is particularly preferred.

[0097] Regarding the addition reaction of polybasic acid monohydric anhydride, a known method can also be used, under the same conditions as the addition reaction of unsaturated monobasic acid to epoxy compounds, to continue the reaction and obtain the target product. The amount of addition of the polybasic acid monohydric anhydride component is preferably such that the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is in the range of 10-150 mgKOH / g, and more preferably in the range of 20-140 mgKOH / g. By setting the value above the lower limit mentioned above, there is a tendency for improved alkali developability. Furthermore, by setting the value below the upper limit mentioned above, there is a tendency for improved curing properties.

[0098] The resulting epoxy (meth)acrylate resin (A1-1) typically has an acid value of 10 mgKOH / g or higher, preferably 50 mgKOH / g or higher, more preferably 80 mgKOH / g or higher, more preferably 200 mgKOH / g or lower, and more preferably 150 mgKOH / g or lower. Setting the acid value above the aforementioned lower limit tends to improve developability. Furthermore, setting the acid value below the aforementioned upper limit tends to improve alkali resistance. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10~200 mgKOH / g, more preferably 50~200 mgKOH / g, and even more preferably 80~150 mgKOH / g.

[0099] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (A1-1), determined by gel permeation chromatography (GPC) based on polystyrene, is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, and especially preferably 2500 or more. It is also preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, further preferably 8000 or less, and especially preferably 7000 or less. Setting the value to the lower limit or above tends to improve sensitivity, film strength, and alkali resistance. Furthermore, setting the value to the upper limit or below tends to improve developability and resolubility. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1,000 to 20,000, more preferably 1,000 to 15,000, further preferably 1,500 to 10,000, further preferably 2,000 to 8,000, and even more preferably 2,500 to 7,000.

[0100] <Acrylic copolymer resins (A2-1), (A2-2), (A2-3), (A2-4)> As an acrylic copolymer resin, various polymer compounds described in Japanese Patent Application Publication No. 7-207211, Japanese Patent Application Publication No. 8-259876, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-140144, Japanese Patent Application Publication No. 11-174224, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2003-233179, and Japanese Patent Application Publication No. 2007-270147 may be used. Among these, resin (A2-1) is particularly preferred.

[0101] (A2-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of (meth)acrylate containing epoxy groups and other free radical polymerizable monomers, or by adding a polybasic acid monohydric anhydride to at least a portion of the hydroxyl groups generated by the addition reaction. (A2-2): A linear, alkali-soluble resin whose main chain contains carboxyl groups. (A2-3): A resin obtained by adding an unsaturated compound containing an epoxy group to the carboxyl group of the resin in (A2-2) above. (A2-4): (Meth)acrylic resin.

[0102] From the viewpoint of sensitivity, the photosensitive resin composition of the present invention is preferably an alkali-soluble resin containing at least one of (A1-1), (A2-1), and (A2-3) as an vinyl unsaturated group. From the viewpoint of surface curing properties, the photosensitive resin composition of the present invention is particularly preferably an alkali-soluble resin containing (A1-1) as an epoxy (meth)acrylate resin as an vinyl unsaturated group.

[0103] (A) The content ratio of alkali-soluble resin is not particularly limited, but relative to the total solid content of the photosensitive resin composition, it is generally 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, generally 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and especially preferably 25% by mass or less. By setting it to the lower limit or above, there is a tendency for the unexposed area to have good solubility in the developer. Furthermore, by setting it to the upper limit or below, there is a tendency for excessive penetration of the developer into the exposed area to be suppressed, and the sharpness or adhesion of the image to be good. The above upper and lower limits can be combined arbitrarily. For example, it is preferred to be 5 to 90% by mass, more preferably 5 to 70% by mass, further preferably 10 to 50% by mass, further preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass. Furthermore, as described above, when the photosensitive resin composition of the present invention contains other alkali-soluble resins as (A) alkali-soluble resins, it is preferable to contain at least one of (A1-1), (A2-1), (A2-2), (A2-3) and (A2-4) mentioned above. When the photosensitive resin composition of the present invention contains other alkali-soluble resins, from the viewpoint of photoresist pattern forming, the content ratio of such resins is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, or may be absent, relative to the total amount of (A) alkali-soluble resins.

[0104] <(B) Photopolymerizable monomers> The photosensitive resin composition of the present invention contains (B) a photopolymerizable monomer in terms of sensitivity and other aspects. Examples of (B) photopolymerizable monomers include compounds having at least one vinyl unsaturated group within the molecule (hereinafter sometimes referred to as "vinyl monomers"). Specifically, examples include (meth)acrylic acid, alkyl (meth)acrylates, acrylonitrile, styrene, and esters of carboxylic acids and polyhydric or monohydric alcohols having one vinyl unsaturated bond.

[0105] As a photopolymerizable monomer (B), it is particularly preferred to use a polyfunctional vinyl monomer having two or more vinyl unsaturated groups per molecule. The number of vinyl unsaturated groups in the polyfunctional vinyl monomer is generally two or more, preferably three or more, more preferably four or more, and even more preferably five or more, particularly six or more, and generally ten or less, preferably eight or less. By setting the value to the lower limit or above, there is a tendency for the photosensitive resin composition to become highly sensitive; conversely, by setting the value to the upper limit or below, there is a tendency for the hardening shrinkage during polymerization to decrease. The above upper and lower limits can be combined arbitrarily. For example, it is better to have 2 to 10, more preferably 3 to 10, further preferably 4 to 10, further preferably 5 to 8, and even more preferably 6 to 8. Examples of polyfunctional vinyl 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 polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

[0106] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, etc., in which the acrylates of these examples are replaced by methacrylates, iconates, butenoates, or maleates.

[0107] Examples of aromatic polyhydroxy compounds and unsaturated carboxylic acids as esters include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and methacrylates of aromatic polyhydroxy compounds. As esters are obtained by the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds, they do not necessarily have to be a single substance. Representative examples include: condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0108] Furthermore, examples of the multifunctional vinyl monomers used in this invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate or by reacting a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reactions of polyepoxides with hydroxyl (meth)acrylates or (meth)acrylic acid; acrylamides such as ethyl bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate. One of these may be used alone, or two or more may be used together.

[0109] (B) The content ratio of photopolymerizable monomers is not particularly limited, but relative to the total solid content of the photosensitive resin composition, it is generally 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and especially preferably 10% by mass or less. By keeping the content of photopolymerizable monomers below the above-mentioned upper limit, there is a tendency for the developer to have adequate penetration into the exposed area, resulting in a good image. The content of photopolymerizable monomer (b) is generally 1% by mass or more, preferably 5% by mass or more. By setting it to the above-mentioned lower limit or more, there is a tendency for photocuring by ultraviolet irradiation to be improved and alkaline developability to also become good. The above upper and lower limits can be combined arbitrarily. For example, it is preferred to be 1~90% by mass, more preferably 1~70% by mass, further preferably 1~50% by mass, further preferably 5~30% by mass, even more preferably 5~20% by mass, and especially preferably 5~10% by mass.

[0110] <(C) Photopolymerization initiator> The photosensitive resin composition of this invention contains (C) a photopolymerization initiator. The photopolymerization initiator is a component that directly absorbs light to induce a decomposition reaction or a hydrogen abstraction reaction, generating polymerization-active free radicals. Sensitizing pigments and other additives may be added as needed.

[0111] Examples of photopolymerization initiators include: metallocene compounds containing dititanium compounds as described in Japanese Patent Application Publications Nos. 59-152396 and 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated diazole derivatives, halomethyl-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and other free radical activators and α-aminoalkyl phenyl ketone derivatives as described in Japanese Patent Application Publication No. 10-39503; and oxime ester derivatives as described in Japanese Patent Application Publications Nos. 2000-80068 and 2006-36750.

[0112] Examples of titanium diacene derivatives include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,4,6-trifluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,6-difluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,4-difluorobenzene-1-yl) titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl) titanium, bis(methylcyclopentadienyl)bis(2,6-difluorobenzene-1-yl) titanium, and dicyclopentadienyl[2,6-difluoro-3-(pyrrole-1-yl)-phenyl-1-yl] titanium.

[0113] Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0114] Examples of halomethylated acediazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-acediazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-acediazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4-acediazole, and 2-trichloromethyl-5-furanyl-1,3,4-acediazole.

[0115] Examples of halomethyl-trisyl derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-trisyl, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-trisyl, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-trisyl, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-trisyl.

[0116] Examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-ointrinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-ointrinylphenyl)butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminoacetophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminophenylmethylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0117] As photopolymerization initiators, oxime derivatives (oxime esters and ketoxime esters) are particularly useful in terms of sensitivity. Among oxime derivatives, oxime esters are preferred from the viewpoint of adhesion to the substrate. However, when using alkali-soluble resins containing phenolic hydroxyl groups, there are disadvantages in terms of sensitivity.

[0118] Oxime esters, as photopolymerization initiators, possess structures that simultaneously absorb ultraviolet light, transmit light energy, and generate free radicals. Therefore, they can achieve high sensitivity with minimal amounts and are thermally stable, allowing for the design of highly sensitive photosensitive resin compositions. In particular, from the perspective of light absorption by i-rays (365 nm) from exposure sources, oxime esters containing substituted carbazole groups (substitutable groups with a carbazole ring) exhibit superior structural characteristics. Currently, the market demands high opacity and black matrices for thin films, leading to increasingly higher pigment concentrations. This makes them especially effective in such situations.

[0119] Examples of oxime ester compounds include compounds containing the structural moiety represented by the following general formula (22), and more preferably, oxime ester compounds represented by the following general formula (23).

[0120] [Chemistry 16]

[0121] In the above formula (22), R 22 represents substituted alkyl with 2 to 12 carbon atoms, heteroarylalkyl with 1 to 20 carbon atoms, alkenyl with 3 to 25 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl with 3 to 20 carbon atoms, aminoalkylcarbonyl with 2 to 10 carbon atoms, aryl with 7 to 20 carbon atoms, heteroaryl with 1 to 20 carbon atoms, alkoxycarbonyl with 2 to 10 carbon atoms, or aryloxycarbonyl with 7 to 20 carbon atoms.

[0122] [Chemistry 17]

[0123] In formula (23), R 21a represents hydrogen or a substituted 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 having 1 to 20 carbon atoms, or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkoxyalkyl group having 3 to 8 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroarylalkyl 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. R 21b represents any substituent containing an aromatic ring or a heteroaromatic ring.

[0124] Furthermore, R 21a can form a ring together with R 21b, and the linking group can be exemplified by: alkyl groups having 1 to 10 carbon atoms, polyethyl (-(CH=CH)r-), polyethynyl (-(C≡C)r-), or groups formed by combining the above (where r is an integer from 0 to 3). R 22a represents the same basis as R 22 in the above equation (22). R 22 in the above general formula (22) and R 22a in the above general formula (23) are preferably alkyl groups with 2 to 12 carbons, heteroarylalkyl groups with 1 to 20 carbons, or cycloalkyl groups with 3 to 8 carbons.

[0125] R 21a in the above general formula (23) is preferably an unsubstituted straight-chain alkyl or cycloalkyl group such as methyl, ethyl, or propyl, or a propyl group substituted with N-acetylated-N-acetylated amino group. Furthermore, R 21b in the above general formula (23) is preferably a substituted carbazole group or a substituted 9-oxosulfur group. The group is a substituted phenyl sulfide group.

[0126] As a photopolymerization initiator for oxime ester compounds, considering the above reasons, it is preferable that R 21b in the above general formula (23) is a substituted carbazolyl group. More preferably, it is a carbazolyl group having at least one group selected from the group consisting of aryl groups with 6 to 25 substituted carbon atoms, aryl carbonyl groups with 7 to 25 substituted carbon atoms, heteroaryl groups with 5 to 25 substituted carbon atoms, heteroaryl carbonyl groups with 6 to 25 substituted carbon atoms, and nitro groups. It is particularly preferred that it is a carbazolyl group having at least one group selected from the group consisting of benzoyl, tolyl, naphthyl, thiophenyl carbonyl, and nitro groups. Furthermore, these groups are preferably bonded to the 3-position of the carbazolyl group.

[0127] Commercially available photopolymerization initiators for this type of oxime ester compound include: OXE-02 manufactured by BASF, and TR-PBG-304 or TR-PBG-314 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0128] Examples of preferred oxime ester compounds used as photopolymerization initiators in this invention include, but are not limited to, the compounds listed below.

[0129] [Chemistry 18]

[0130] [Chemistry 19]

[0131] [Chemistry 20]

[0132] Examples of ketoxime ester compounds include compounds containing the structural moiety represented by the following general formula (24), and more preferably ketoxime ester compounds represented by the following general formula (25).

[0133] [Chemistry 21]

[0134] In the above general formula (24), R 24 has the same meaning as R 22 in the above general formula (22).

[0135] [Chemistry 22]

[0136] In the above general formula (25), R 23a represents a substituted phenyl, 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 a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkoxyyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkoxyyl group having 3 to 8 carbon atoms, an arylyl group having 7 to 20 carbon atoms, a heteroarylyl 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.

[0137] R 23b represents any substituent containing an aromatic ring or a heteroaromatic ring. Furthermore, R 23a can form a ring together with R 23b, and the linking group can be exemplified by: alkyl groups having 1 to 10 carbon atoms, polyethyl (-(CH=CH)r-), polyethynyl (-(C≡C)r-), or groups formed by combining the above (where r is an integer from 0 to 3).

[0138] R 24a represents substituted alkyl (2-12 carbons), alkenyl (3-25 carbons), cycloalkanyl (4-8 carbons), benzoyl (7-20 carbons), heteroaryl (3-20 carbons), alkoxycarbonyl (2-10 carbons), aryloxycarbonyl (7-20 carbons), heteroaryl (2-20 carbons), or alkylaminocarbonyl (2-20 carbons). Examples of R 24 in the above general formula (24) and R 24a in the above general formula (25) are preferably: alkyl group with 2 to 12 carbons, heteroarylalkyl group with 1 to 20 carbons, cycloalkyl group with 3 to 8 carbons, and aryl group with 7 to 20 carbons.

[0139] R 23a in the above general formula (25) is preferably exemplified as: unsubstituted ethyl, propyl, butyl or ethyl or propyl substituted with methoxycarbonyl. Furthermore, as R 23b in the above general formula (25), preferably examples include: a substituted carbazole group or a substituted phenyl sulfide group. Preferred ketooxime ester compounds in this invention include, but are not limited to, the following examples.

[0140] [Chemistry 23]

[0141] [Chemistry 24]

[0142] [Chemistry 25]

[0143] Commercially available photopolymerization initiators for this type of ketoxime ester compound include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0144] These oxime and ketoxime ester compounds are known compounds in themselves, for example, one of a series of compounds described in Japanese Patent Application Publication No. 2000-80068 or Japanese Patent Application Publication No. 2006-36750. The above-mentioned photopolymerization initiators can be used alone or in combination with two or more.

[0145] In addition, 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-tert-butylanthraquinone, and 1-chloroanthraquinone; and benzophenone derivatives such as benzophenone, milchnerone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2, 2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-hydroxylinyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone and other acetophenone derivatives; 9-oxothiophene 2-Ethyl-9-oxosulfur 2-Isopropyl-9-oxosulfur 2-Chloro-9-oxosulfur 2,4-Dimethyl-9-oxosulfur 2,4-Diethyl-9-oxosulfur 2,4-Diisopropyl-9-oxosulfur 9-Oxysulfur Derivatives; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenanthrene derivatives such as 9,10-dimethylbenzophenone; anthrone derivatives such as benzo[anthrone]. Among these photopolymerization initiators, oxime ester derivatives are particularly preferred for the reasons mentioned above.

[0146] <Sensitizing Pigments> As needed, to improve sensitivity, a sensitizing pigment corresponding to the wavelength of the light source used for image exposure can be incorporated into the photopolymerization initiator. Examples of such sensitizing pigments include those described in Japanese Patent Application Publication No. 4-221958 and Japanese Patent Application Publication No. 4-219756. Pigments, heterocyclic coumarin pigments described in Japanese Patent Application Publication No. 3-239703 and No. 5-289335, 3-ketocoumarin compounds described in Japanese Patent Application Publication No. 3-239703 and No. 5-289335, and pyrrole methylene pigments described in Japanese Patent Application Publication No. 6-19240, and also exemplified by: Japanese Patent Application Publication No. 47-2528, Japanese Patent Application Publication No. 54-155292, and Japanese Patent Application Publication No. 45-37377, etc. Pigments having a dialkylaminobenzene skeleton as described in Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, Japanese Patent Application Publication No. 59-56403, Japanese Patent Application Publication No. 2-69, Japanese Patent Application Publication No. 57-168088, Japanese Patent Application Publication No. 5-107761, Japanese Patent Application Publication No. 5-210240, and Japanese Patent Application Publication No. 4-288818.

[0147] Among these sensitizing pigments, those containing an amino group are preferred, and those having both an amino group and a phenyl group within the same molecule are even more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are further preferred; 2-(p-dimethylaminophenyl)benzo[4,5]benzo[5]benzo[6,7 ... Compounds containing p-dialkylaminophenyl groups, such as 4-acetazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)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, are preferred, especially 4,4'-dialkylaminobenzophenone. Sensitizing pigments can be used alone or in combination with two or more.

[0148] (C) The content of the photopolymerization initiator is not particularly limited, but relative to the total solid content of the photosensitive resin composition, it is generally 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, generally 30% by mass or less, preferably 20% by mass or less, even 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 the lower limit or above, there is a tendency for increased sensitivity. Furthermore, by setting it to the upper limit or below, there is a tendency for increased solubility of the unexposed portion in the developer. The above upper and lower limits can be combined arbitrarily. For example, it is preferred to be 1~30% by mass, more preferably 1~20% by mass, further preferably 2~15% by mass, further preferably 3~10% by mass, and even more preferably 4~8% by mass.

[0149] When using sensitizing pigments, the proportion of the sensitizing pigments in the photosensitive resin composition is typically 0-20% by mass, preferably 0-15% by mass, and even more preferably 0-10% by mass, out of the total solids content of the photosensitive resin composition.

[0150] <(D) Pigment> When the photosensitive resin composition of the present invention is used for forming pixels, black matrices, or colored spacers in color filters, it is preferably found to contain a (D) colorant. A colorant refers to the component that colors the photosensitive resin composition of the present invention. Dyes or pigments can be used as colorants; however, pigments are preferred in terms of heat resistance and lightfastness.

[0151] As pigments, various colors can be used, including blue, green, red, yellow, purple, orange, brown, and black. Furthermore, their structures can utilize organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, diazonium, indanthrene, and perylene pigments. Various inorganic pigments can also be used.

[0152] The following describes specific examples of pigments that can be used in this invention, indicated by pigment designations. Furthermore, the terms "CI Pigment Red 2" and similar examples used below refer to the Dye 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, 53: 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, 1 49, 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, 23 2, 233, 235, 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, 276. Among them, CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is preferred, and CI Pigment Red 177, 209, 224, 254 is even more preferred.

[0153] 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 even more preferred.

[0154] 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. Among these, CI pigment green 7, 36, and 58 are preferred.

[0155] 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, 1 34, 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. Among them, 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 even more preferred.

[0156] 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. Among these, CI Pigment Orange 38, 64, and 71 are preferred.

[0157] Examples of CI pigments for purple include: 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 pigments 19, 23, and 29 are preferred, and CI pigments 23 and 29 are even more preferred.

[0158] 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 pigment can be used as the (D) pigment. The black pigment can be a single black pigment, or a mixture of red, green, blue pigments, etc. Furthermore, such pigments can be appropriately selected from inorganic or organic pigments and dyes. As for pigments that can be mixed for the preparation of black pigments, examples include: Victoria Pure Blue (42595), Auramine O (41000), Cathione Brilliant Yellow (Alkaline 13), Rose Red 6GCP (45160), Rose Red B (45170), Safranbolu OK70:100 (50240), Wool Poppy Red X (42080), No.120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), Smüller Daylight Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Smüller Daylight Red 4015 (12355), Leonor Red 7B4401 (15850), Fastgen Blue. TGR-L (74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15:6), Leonogen Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36) (Furthermore, the numbers in parentheses above refer to the dye index (CI)).

[0159] Furthermore, if we use CI numbers to represent other pigments that can be mixed, we can list, for example: 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 Purple Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64, CI Green Pigment 7, CI Brown Pigment 23, 25, 26.

[0160] Examples of black pigments that can be used alone include: carbon black, acetylene black, lampblack, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and acetylene black. When using black pigments in these (D) pigments, carbon black is preferable from the viewpoint of light-blocking rate and image characteristics. Examples of carbon black include the following.

[0161] Manufactured by Mitsubishi Chemical: 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 below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, 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 manufactures: Monarch (registered trademark; hereinafter the same) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark; hereinafter the same) 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 Manufactured by Birla: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RA VEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0162] Other examples of black pigments include titanium black, aniline black, iron oxide black pigments, and mixtures of red, green, and blue organic pigments.

[0163] As pigments, barium sulfate, lead sulfate, titanium dioxide, litharge, iron oxide, and chromium oxide can also be used, for example. Multiple of these pigments can also be used in combination. For example, to adjust chromaticity, green and yellow pigments can be used together, or blue and purple pigments can be used together.

[0164] When used as the coloring layer for a color filter, the average particle size of the pigment is not particularly limited as long as it achieves the desired color rendering. It varies depending on the type of pigment used, but is preferably in the range of 10-100 nm, and more preferably in the range of 10-70 nm. By ensuring the average particle size of the pigment falls within the aforementioned range, there is a tendency to achieve high-quality color characteristics in liquid crystal display devices manufactured using the photosensitive resin composition of this invention. The average particle size of carbon black is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or more, for example, preferably 20 to 50 nm, and more preferably 20 to 60 nm. By keeping the average particle size below the above-mentioned upper limit, there is a tendency to reduce scattering and suppress the decrease in color properties such as light-blocking properties or contrast. Furthermore, by keeping the average particle size above the above-mentioned lower limit, there is a tendency to achieve good dispersibility without requiring an excessive amount of dispersant. Furthermore, the average particle size of the aforementioned pigments, including carbon black, can be obtained by directly measuring the size of primary particles from electron microscope images. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and their average value is taken as the particle size. Next, for more than 100 particles, the volume (mass) of each particle is calculated by approximating a cuboid with the obtained particle size, and the volume-average particle size is determined and taken as the average particle size. Furthermore, the same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0165] When the photosensitive resin composition of the present invention contains (D) pigment, it is preferable to contain at least a pigment as a pigment. Alternatively, dyes may be used in combination within a range that does not affect the effects of the present invention. Examples of dyes that can be used in combination include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene dyes.

[0166] 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.

[0167] Examples of anthraquinone dyes include: CI Variant 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. In addition, examples of phthalocyanine dyes include CI Vat Blue 5, examples of quinone imine dyes include CI Basic Blue 3 and CI Basic Blue 9, examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

[0168] When the photosensitive resin composition of the present invention contains (D) pigment, the content ratio of (D) pigment relative to the total solid content in the photosensitive resin composition is generally selected in the range of 1 to 70% by mass. Within this range, it is more preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and even more preferably 60% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferred to be 1~70% by mass, more preferably 20~70% by mass, further preferably 30~60% by mass, and even more preferably 40~60% by mass.

[0169] The photosensitive resin composition of the present invention can be used for various applications as described below. When used for forming a black matrix, it can be used as the (D) colorant by using the aforementioned black colorant such as carbon black or titanium black, or by mixing several colorants other than black and adjusting them to black before use. Among these, carbon black is particularly preferred from the viewpoint of dispersion stability and light-blocking properties.

[0170] When the photosensitive resin composition of the present invention is used in the formation of a black matrix, it is necessary to increase the concentration of black pigment to improve the opacity. From this perspective, the content ratio of black pigment relative to the total solid content of the photosensitive resin composition is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more. 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 above upper and lower limits can be combined arbitrarily. For example, it is preferably 40~70% by mass, more preferably 45~70% by mass, and even more preferably 50~65% by mass.

[0171] When the photosensitive resin composition of the present invention contains (D) pigment, the content ratio of (D) pigment relative to 100 parts by mass of (A) alkali-soluble resin is typically 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably 60 parts by mass or more, further preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and typically 500 parts by mass or less, preferably 300 parts by mass or less, and more preferably 280 parts by mass or less. By setting the content ratio of (D) pigment to the above-mentioned lower limit value or above, there is a tendency to easily suppress the decrease in the solubility of the unexposed area in the developer. Furthermore, by setting it to the above-mentioned upper limit value or below, there is a tendency to easily obtain the desired image film thickness. The above upper and lower limits can be combined arbitrarily. For example, it is preferable to be 20 to 500 parts by mass, more preferably 30 to 500 parts by mass, further preferably 40 to 500 parts by mass, further preferably 60 to 300 parts by mass, even more preferably 80 to 300 parts by mass, particularly preferably 120 to 280 parts by mass, and most preferably 160 to 280 parts by mass.

[0172] <Dispersant> In cases where the photosensitive composition of the present invention contains (D) pigment, in order to ensure the stability of quality, it is important to finely disperse the pigment and stabilize the dispersion state, and therefore it is preferable to further contain a dispersant. As a dispersant, a polymeric dispersant with functional groups is preferred. Furthermore, in terms of dispersion stability, a polymeric dispersant with functional groups such as carboxyl groups, phosphate groups, sulfonic acid groups, or their salts, primary, secondary, or tertiary amino groups, quaternary ammonium salt groups, or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine is particularly preferred. Among these, polymeric dispersants with basic functional groups such as primary, secondary, or tertiary amino groups, quaternary ammonium salt groups, or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are especially preferred. Using such polymeric dispersants with basic functional groups tends to improve dispersibility.

[0173] Examples of polymeric dispersants include: carbamate dispersants, acrylic dispersants, polyethylene imine dispersants, polyallylamine dispersants, dispersants containing monomers and macromonomers with amine groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0174] Specific examples of such dispersants include the following trade names: EFKA (registered trademark; manufactured by Efka Chemicals BV (EFKA) Co., Ltd.), Disperbyk (registered trademark; manufactured by BYK-Chemie Co., Ltd.), Disparlon (registered trademark; manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark; manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Flowlen (registered trademark; manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark; manufactured by Ajinomoto Fine-Techno Co., Ltd.). These polymeric dispersants can be used alone or in combination of two or more.

[0175] Of these, in terms of adhesion and linearity, the dispersant is preferably a urethane-based polymeric dispersant and / or an acrylic polymeric dispersant containing basic functional groups; in terms of adhesion, it is more preferably a urethane-based polymeric dispersant. Furthermore, in terms of dispersibility and shelf life, it is preferably a polymeric dispersant containing basic functional groups and polyester and / or polyether bonds.

[0176] The weight average molecular weight (Mw) of the polymeric dispersant is typically 700 or higher, preferably 1000 or higher, and typically 100,000 or lower, preferably 50,000 or lower, and even more preferably 30,000 or lower. By setting it below the above upper limit, there is a tendency for alkaline developability to become good even at higher pigment concentrations. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 700~100000, more preferably 700~50000, and even more preferably 1000~30000. Examples of urethane and acrylic polymeric dispersants include: Disperbyk 160~167, 182 series (all urethane-based), and Disperbyk 2000, 2001 (all acrylic-based) (all manufactured by BYK-Chemie). Among the most preferred urethane-based polymeric dispersants having basic functional groups, polyester and / or polyether bonds, and a weight average molecular weight of 30,000 or less, are Disperbyk 167 and 182.

[0177] <Carbamate-based polymeric dispersants> As a carbamate-based polymeric dispersant, a preferred chemical structure can be specifically illustrated by, for example, a dispersing resin 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 compound having active hydrogen and tertiary amine groups in the same molecule.

[0178] Examples of the aforementioned polyisocyanate compounds include: aromatic diisocyanates such as phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and bitoluidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate; 4,4'-methylene bis(cyclohexyl) isocyanate; and ω,ω'-diisocyanate groups. Alicyclic diisocyanates such as dimethylcyclohexane, alicyclic diisocyanates such as phenyl diisocyanate and α,α,α',α'-tetramethylphenyl diisocyanate, aliphatic diisocyanates having aromatic rings, lysine triisocyanates, 1,6,11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate, and other triisocyanates, as well as trimers, hydrates, and polyol adducts of the above. As polyisocyanates, trimers of organic diisocyanates are preferred, and most preferably trimers of toluene diisocyanate and isophorone diisocyanate. These can be used alone or in combination of two or more.

[0179] As a method for manufacturing isocyanate trimers, the following method can be used: using a suitable trimerizing catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., to partially trimerize the isocyanate groups of the above-mentioned polyisocyanates; after the trimerization is stopped by adding a catalyst poison, the unreacted polyisocyanates are removed by solvent extraction and thin-film distillation, thereby obtaining the target polyisocyanate containing isocyanurate groups.

[0180] Examples of compounds having one or two hydroxyl groups in the same molecule with an average molecular weight of 300 to 10,000 include: polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, etc., and compounds obtained by alkanolysing a single terminal hydroxyl group of such compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more such compounds.

[0181] Examples of polyether glycols include: polyether glycols, polyether ester glycols, and mixtures of two or more thereof. Examples of polyether glycols include those obtained by homopolymerization or copolymerization of epoxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more thereof.

[0182] Examples of polyether diols include those obtained by reacting an ether-containing diol or a mixture of other diols with a dicarboxylic acid or such anhydride, or by reacting an epoxide with a polyester diol, such as poly(polyoxytetramethylene) adipate. Preferably, polyether diols are compounds obtained by alkanolysing a single terminal hydroxyl group of polyethylene glycol, polypropylene glycol, polyoxytetramethylene diol, or such compounds with an alkyl group having 1 to 25 carbon atoms.

[0183] Examples of polyester diols include: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides reacted with diols (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, neopentanediol, 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). Polyols obtained by polycondensation of aliphatic diols such as diols, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol, alicyclic diols such as dihydroxymethylcyclohexane, aromatic diols such as benzenediethanol and dihydroxyethoxybenzene, and N-alkyldialkylolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate, or polylactone diols or monohydric alcohols obtained by using the above-mentioned diols or alcohols with 1 to 25 carbon atoms as initiators, such as polycaprolactone diol, polymethylvalerol, and mixtures of two or more of the above. Polycaprolactone diol or polycaprolactone in which an alcohol with 1 to 25 carbon atoms is used as an initiator is preferred.

[0184] Examples of polycarbonate diols include poly(1,6-hexanediol) ester and poly(3-methyl-1,5-pentanediol) ester; examples of polyolefin diols include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol. One of these may be used alone, or two or more may be used together.

[0185] The average molecular weight of compounds having one or two hydroxyl groups within the same molecule is typically 300 to 10,000, preferably 500 to 6,000, and even more preferably 1,000 to 4,000. Next, compounds containing both active hydrogen and tertiary amine groups within the same molecule will be described. Active hydrogen refers to hydrogen atoms directly bonded to oxygen, nitrogen, or sulfur atoms. Examples of active hydrogen include hydrogen atoms in functional groups such as hydroxyl, amino, and thiol groups. Among these, hydrogen atoms in amino groups are preferred, and hydrogen atoms in primary amine groups are particularly preferred.

[0186] There are no particular limitations on the tertiary amino group. For example, examples include amino groups with alkyl groups having 1 to 4 carbon atoms or heterocyclic structures. More specifically, examples include imidazole rings or triazole rings. Examples of compounds containing both active hydrogen and tertiary amine groups within 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.

[0187] Examples of nitrogen-containing heterocycles where the tertiary amine group is a nitrogen-containing heterocyclic structure include: pyrazole rings, imidazole rings, triazole rings, tetraazole rings, indole rings, carbazole rings, indazole rings, benzimidazole rings, benzotriazole rings, benzothiazole rings, benzothiazolium rings, benzothiadiazole rings, and other nitrogen-containing heterocyclic 5-membered rings; pyridine rings, pyrazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings, isoquinoline rings, and other nitrogen-containing heterocyclic 6-membered rings. Among these nitrogen-containing heterocycles, imidazole rings or triazole rings are preferred.

[0188] Examples of compounds having such imidazole rings and amino groups include: 1-(3-aminopropyl)imidazolium, histidine, 2-aminoimidazolium, and 1-(2-aminoethyl)imidazolium. Examples of compounds having such triazole rings and amino groups 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. Among them, 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.

[0189] One of these may be used alone, or two or more may be used together. The preferred formulation ratio of raw materials for manufacturing carbamate-based polymeric dispersants is as follows: relative to 100 parts by mass of a polyisocyanate compound, a compound having one or two hydroxyl groups per molecule with an average molecular weight of 300 to 10,000 is 10 to 200 parts by mass, more preferably 20 to 190 parts by mass, and even more preferably 30 to 180 parts by mass; and a compound having active hydrogen and tertiary amine groups per molecule is 0.2 to 25 parts by mass, more preferably 0.3 to 24 parts by mass.

[0190] The manufacture of urethane-based polymeric dispersants is based on known methods for manufacturing polyurethane resins. Solvents used in the manufacturing process may include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and acetic acid solvents; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, dibutanol, and terbutanol; chlorides such as dichloromethane and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. One or more of these solvents may be used individually or in combination.

[0191] In the above manufacturing process, a carbamate reaction catalyst is typically used. Examples of such catalysts include one or more of the following: tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctanoate, and stannous octoate; iron-based catalysts such as ferric acetopyruvate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0192] <Methods for determining amine value> The tertiary amine value of a dispersant is expressed as the mass of KOH equivalent to 1 g of alkali in the dispersant sample containing solvent-removed solids, and can be determined by the following method. Accurately weigh 0.5–1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titration apparatus equipped with a pH electrode, neutralize and titrate the solution with a 0.1 mol / L HClO₄ (perchloric acid) acetic acid solution. Use the inflection point of the pH titration curve as the titration endpoint, and calculate the amine value using the following formula.

[0193] Amine value [mgKOH / g] = (561 × V) / (W × S) [W represents: the amount of dispersant sample weighed [g], V represents: the titration volume at the titration endpoint [mL], and S represents: the concentration of solids in the dispersant sample [mass %]] The amount of compounds containing both active hydrogen and tertiary amine groups within the same molecule is preferably controlled to result in an amine value in the range of 1–100 mg KOH / g after the reaction. More preferably, it is in the range of 5–95 mg KOH / g. The amine value is a value expressed in milligrams of KOH corresponding to the acid value obtained by titrating a basic amine group with an acid. By setting the amine value above the aforementioned lower limit, there is a tendency for improved dispersibility. Furthermore, by setting it below the aforementioned upper limit, there is a tendency for improved developability.

[0194] When isocyanate groups remain in the polymeric dispersant due to the above reaction, if the isocyanate groups are then consumed by alcohol or amine compounds, the product's long-term stability becomes higher, thus making it better. The weight-average molecular weight (Mw) of carbamate-based polymeric dispersants is typically in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. It is particularly preferred to be below 30,000. By setting the value above the aforementioned lower limit, there is a tendency for improved dispersibility and dispersion stability. Furthermore, by setting the value below the aforementioned upper limit, there is a tendency for improved solubility. The aforementioned upper and lower limits can be arbitrarily combined. For example, they can be 1,000 to 30,000, 2,000 to 30,000, or 3,000 to 30,000. If the molecular weight is below 30,000, there is a tendency for improved alkaline developability, especially at higher pigment concentrations. Examples of such preferred commercially available carbamate dispersants include Disperbyk 167 and 182 (BYK-Chemie).

[0195] When the photosensitive resin composition of the present invention contains a dispersant, the proportion of the dispersant in the total solids component of the photosensitive resin composition is generally 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, generally 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and even more preferably 10% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 50% by mass, more preferably 3 to 50% by mass, further preferably 5 to 30% by mass, further preferably 7 to 30% by mass, and even more preferably 10 to 20% by mass. Furthermore, the content ratio of the dispersant relative to 100 parts by weight of the (D) pigment is typically 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more, typically 200 parts by weight or less, preferably 80 parts by weight or less, more preferably 50 parts by weight or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 200 parts by weight, more preferably 10 to 80 parts by weight, and even more preferably 15 to 50 parts by weight. By setting the value above the aforementioned lower limit, there is a tendency to easily ensure sufficient dispersion. Furthermore, by setting the value below the aforementioned upper limit, there is a tendency to easily achieve sufficient color density, sensitivity, and film-forming properties without reducing the ratio of other components.

[0196] <Thiols> For the photosensitive resin composition of the present invention, in order to achieve high sensitivity and improved adhesion to the substrate, it is preferable to contain thiols. Examples of thiols include: hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene glycol dithiopropionate, butylene glycol dithioacetate, ethylene glycol dithioacetate, trimethylolpropane trithioacetate, butylene glycol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butylene glycol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyroxyloxy)butane; (trade name: Karenz MT) BD1 (manufactured by Showa Denko), butylene glycol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate); (trade name: Karenz MT PE1, manufactured by Showa Denko), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butylene glycol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko). Each of these can be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferred, and Karenz MT PE1 is especially preferred.

[0197] When using thiol compounds, the content of the thiol compounds relative to the total solid content of the photosensitive resin composition of the present invention 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, typically 10% by mass or less, and preferably 5% by mass or less. By setting it to the lower limit or above, there is a tendency to suppress the decrease in sensitivity. Furthermore, by setting it to the upper limit or below, there is a tendency to easily achieve good storage stability. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1~10% by mass, more preferably 0.3~10% by mass, and even more preferably 0.5~5% by mass.

[0198] Solvent The photosensitive resin composition of the present invention is generally used in a state in which various materials containing (A) alkali-soluble resin, (B) photopolymerizable monomer and (C) photopolymerization initiator, and (D) colorant used as needed are dissolved or dispersed in an organic solvent. As a solvent, sometimes the organic solvent used in the manufacturing method of the present invention or the organic solvent contained in the carboxyl-containing resin of the present invention are used directly. As an organic solvent, it is preferable to select one with a boiling point (under a pressure of 1013.25 [hPa]; the same applies to boiling point below) in the range of 100 to 300 °C. More preferably, it is a solvent with a boiling point of 120 to 280 °C. Examples of such organic solvents include the following.

[0199] 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 tributyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and other similar diol monoalkyl ethers;

[0200] Diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and other dialkyl glycol ethers; 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 diol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

[0201] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl pentyle ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyle ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentyle ketone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, 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 bicyclohexane;

[0202] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; 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 octanoate, 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 are chain or cyclic esters. Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0203] Halogenated hydrocarbons such as chlorobutane and chloropentane; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Commercially available solvents that fall under the category of the aforementioned solvents include, for example: mineral spirit, Varsol#2, Apco#18 Solvent, Apco diluent, 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 diethylene glycol dimethyl ether (all trade names).

[0204] These organic solvents can be used alone or in combination of two or more. When forming pixels or black matrices of a color filter using photolithography, the organic solvent preferably has a boiling point in the range of 100 to 250°C. More preferably, it has a boiling point in the range of 120 to 230°C. Among the aforementioned organic solvents, diol alkyl ether acetates are preferred in terms of good balance between coatability and surface tension, as well as high solubility of the constituent components in the composition.

[0205] Diol alkyl ether acetates can be used alone or in combination with other organic solvents. Among these, monoalkyl glycol ethers are particularly preferred, especially in terms of the solubility of the components in the composition. Monoalkyl glycol ethers have high polarity; if added in excessive amounts, the pigment may easily aggregate, leading to increased viscosity and decreased storage stability in the resulting photosensitive resin composition. Therefore, the ratio of monoalkyl glycol ethers in the solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0206] It is also preferable to use organic solvents with a boiling point of 200°C or higher (hereinafter sometimes referred to as "high-boiling-point solvents"). By using such high-boiling-point solvents, the following effects are achieved: the photosensitive resin composition is less prone to drying, preventing the destruction of the uniform dispersion of the pigment in the composition due to rapid drying. That is, it has the following effects, for example: preventing the pigment from precipitating and curing at the tip of the slit nozzle, thus preventing foreign matter defects. In terms of this effect being more desirable, 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-butanediol diacetate, glyceryl triacetate, and 1,6-hexanediol diacetate are particularly preferred.

[0207] The content of high-boiling-point solvents in the organic solvent is preferably 0% to 50% by mass, more preferably 0.5% to 40% by mass, and even more preferably 1% to 30% by mass. By setting it to the lower limit or above, for example, there is a tendency to suppress the precipitation and curing of pigments at the tip of the slit nozzle, which could cause foreign matter defects. Furthermore, by setting it to the upper limit or below, there is a tendency to suppress the slow drying temperature of the composition, which could lead to problems such as poor tact in the reduced pressure drying process during the color filter manufacturing step or pre-baking porosity marks.

[0208] In the photosensitive resin composition of the present invention, the content ratio of organic solvent is not particularly limited. From the viewpoint of ease of coating or 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, and even more preferably 10% by mass or more, and even more 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.

[0209] <Other formulation components of the photosensitive resin composition> In addition to the above-mentioned components, adhesion enhancers, coatability enhancers, pigment derivatives, developer modifiers, ultraviolet absorbers, antioxidants, etc., may also be appropriately formulated into the photosensitive resin composition of the present invention.

[0210] <Seam-bonding enhancer> To improve adhesion to the substrate, it may contain adhesion enhancers, such as silane coupling agents and titanium coupling agents, with silane coupling agents being particularly preferred. Examples of such silane coupling agents include: KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicones), Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray). Furthermore, a single silane coupling agent can be used, or two or more can be used in any combination and ratio. Furthermore, the photosensitive resin composition of the present invention may contain a bonding enhancer other than a silane coupling agent, such as a phosphoric acid bonding enhancer or other bonding enhancers.

[0211] As a phosphoric acid-based bonding enhancer, a phosphate ester containing (meth)acryloxy group is preferred, and those represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0212] [Chemistry 26]

[0213] In the above general formulas (g1), (g2), and (g3), R 51 independently represents a hydrogen atom or a methyl group, l and l' are each an integer from 1 to 10, and m is each 1, 2, or 3. Other examples of adhesion enhancers include TEGO*Add Bond LTH (manufactured by Evonik). These phosphate-containing compounds or other adhesion enhancers can be used alone or in combination of two or more.

[0214] When the photosensitive resin composition of the present invention contains a adhesion enhancer, the content ratio of the adhesion enhancer in the photosensitive resin composition is not particularly limited. It 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, 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. By setting it to the lower limit or above, there is a tendency for improved adhesion. Furthermore, by setting it to the upper limit or below, there is a tendency for improved developability. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01~5% by mass, more preferably 0.01~3% by mass, further preferably 0.1~2% by mass, and even more preferably 0.5~1.5% by mass.

[0215] <Copyability Enhancer> To improve coatability, a surfactant can be included in the photosensitive resin composition of the present invention as a coatability enhancer. For example, anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferred as they are less likely to adversely affect the properties. Fluoropolymer or polysiloxane surfactants are particularly effective in terms of coatability.

[0216] 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), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin Industries), L-77 (manufactured by Nippon Unicar), and FC4430 (manufactured by 3M Japan). Furthermore, a single surfactant can be used, or two or more surfactants can be combined and used in any combination and ratio. When the photosensitive resin composition of the present invention contains a surfactant, the content ratio of the surfactant in the photosensitive resin composition is not particularly limited. Preferably, it is 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1.0% by mass or less, more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less. By setting it to the lower limit or above, there is a tendency for improved photoresist coating uniformity. Furthermore, by setting it to the upper limit or below, there is a tendency for the photoresist sensitivity not to decrease. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01~1.0% by mass, more preferably 0.01~0.7% by mass, further preferably 0.05~0.5% by mass, and even more preferably 0.05~0.3% by mass.

[0217] Pigment Derivatives To improve dispersibility and shelf life, the photosensitive resin composition of the present invention may contain pigment derivatives. Examples of pigment derivatives include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolineone, diazonium, anthraquinone, indanthrene, perylene, pyrene, pyrrolopyrroledione, and diazonium derivatives, among which phthalocyanine and quinophthalone derivatives are preferred.

[0218] Examples of substituents for pigment derivatives include: sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylamino alkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., which are directly or indirectly bonded to the pigment skeleton via alkyl, aryl, or heterocyclic groups, with sulfonic acid groups being preferred. Furthermore, multiple substituents can replace one pigment skeleton. 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 pyrrolopyrroledione, and sulfonic acid derivatives of diazonium. One of these can be used alone, or two or more can be used in combination.

[0219] When the photosensitive resin composition of the present invention contains pigment derivatives, the mixing ratio of the pigment derivatives is not particularly limited. However, relative to the total solid content of the photosensitive resin composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. Furthermore, it is preferably 10% by mass or less, and even more preferably 5% by mass or less. By setting it to the lower limit or above, there is a tendency to improve dispersion stability. Furthermore, by setting it to the upper limit or below, there is a tendency to improve developability. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1~10% by mass, more preferably 0.5~10% by mass, and even more preferably 1.0~5% by mass.

[0220] <Physical Properties of Photosensitive Resin Compositions> The photosensitive resin composition of the present invention is preferably used for forming a black matrix, and from this point of view, it is preferable to present a black color. Furthermore, the optical density (OD) per 1 μm film thickness is preferably 1.0 or higher, more preferably 2.0 or higher, further preferably 2.5 or higher, further preferably 3.0 or higher, particularly preferably 4.0 or higher, most preferably 4.5 or higher, and typically 6.0 or lower, for example, preferably 1.0 to 6.0, more preferably 2.0 to 6.0, further preferably 2.5 to 6.0, further preferably 3.0 to 6.0, particularly preferably 4.0 to 6.0, and most preferably 4.5 to 6.0. By setting it to the above-mentioned lower limit value or higher, there is a tendency to ensure sufficient light-blocking properties.

[0221] <Method for manufacturing photosensitive resin composition> When the photosensitive resin composition of the present invention contains a (D) pigment, it is preferable to pre-disperse the (D) pigment using a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, or the like. Through dispersion, the (D) pigment is micronized, thereby improving the coating characteristics of the photoresist. Furthermore, when using a black pigment as the (D) pigment, it helps to improve the light-blocking ability.

[0222] The dispersion treatment is preferably carried out in a system using (D) pigments, organic solvents, and dispersants as needed, and (A) alkali-soluble resins in part or all of them. (Hereinafter, the mixture supplied to the dispersion treatment and the composition obtained by the dispersion treatment are sometimes referred to as "ink" or "pigment dispersion".) In particular, if a polymeric dispersant is used as the dispersant, the thickening of the obtained ink and photoresist over time can be suppressed (excellent dispersion stability), which is therefore better. When dispersing a liquid containing all the components formulated in a photosensitive resin composition, the heat generated during dispersion may lead to modification of highly reactive components. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymeric dispersant.

[0223] When dispersing (D) pigment using a sand mill, glass beads or zirconia beads with a diameter of approximately 0.1 to 8 mm are preferable. Regarding dispersion conditions, the temperature is typically between 0°C and 100°C, preferably between room temperature and 80°C. The suitable dispersion time varies depending on the liquid composition and the size of the dispersion equipment, and should be adjusted accordingly. The standard for dispersion is to control the ink gloss within the range of 100 to 200 for the 20-degree specular gloss of the photoresist (JIS Z8741). When the gloss of the photoresist is low, the dispersion is insufficient, resulting in more coarse pigment particles remaining, potentially leading to insufficient developability, adhesion, and resolution. Furthermore, if dispersion is performed until the gloss value exceeds the aforementioned range, the pigment breaks down, producing a large number of ultrafine particles, which may actually impair dispersion stability.

[0224] Next, when the photosensitive resin composition contains the components included in the composition, namely (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) pigment, the ink obtained by the above dispersion treatment is mixed at a temperature of 20-30°C to form a homogeneous solution. During the manufacturing process of the photosensitive resin composition, fine impurities often mix into the liquid; therefore, it is ideal to filter the obtained photoresist using a filter or similar device.

[0225] [Ink] The ink manufacturing method of the present invention comprises (A) an alkali-soluble resin, an organic solvent, and (D) a pigment, and further includes: adjusting a carboxyl-containing resin manufactured using the method of the present invention as the (A) alkali-soluble resin. A dispersant may be added to the ink as needed. Organic solvents, (D) pigments and dispersants are preferred for use in photosensitive resin compositions.

[0226] <Ink Manufacturing Methods> The ink of the present invention is obtained, for example, by a dispersion treatment described in the method for manufacturing a photosensitive resin composition.

[0227] [Hardened material] The method for manufacturing the hardened material of the present invention comprises: hardening the photosensitive resin composition obtained by the manufacturing method of the present invention. Cured materials obtained by curing photosensitive resin compositions can be better used as components that constitute color filters, such as pixels, black matrices, or color spacers.

[0228] [Black Matrix] The method for manufacturing a black matrix according to the present invention includes: forming a black matrix using a hardened material obtained by the manufacturing method of the present invention. The use of a black matrix of hardened material obtained by the manufacturing method of the present invention will be described based on the manufacturing method.

[0229] (1) Support As a support for forming the black matrix, the material is not particularly limited as long as it has adequate strength. Transparent substrates are primarily used, and examples of suitable materials include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polyurethane, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic acid resins, and various types of glass. From a heat resistance perspective, glass and heat-resistant resins are preferred. Furthermore, transparent electrodes such as ITO (Indium Tin Oxides) and IZO (Indium Zinc Oxide) can be formed on the surface of the substrate. Besides transparent substrates, they can also be formed on TFT (thin-film transistor) arrays.

[0230] To improve surface properties such as adhesion, the support can be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, and film formation treatment with various resins such as silane coupling agents or urethane resins, as needed. The thickness of the transparent substrate is typically set to 0.05~10 mm, preferably in the range of 0.1~7 mm. Furthermore, when performing thin film formation processes with various resins, the film thickness is typically 0.01~10 μm, preferably in the range of 0.05~5 μm.

[0231] (2) Black Matrix As a method for forming a black matrix by means of a hardened material obtained using the manufacturing method of the present invention, the following method can be exemplified: a photosensitive resin composition obtained using the manufacturing method of the present invention is hardened to obtain a hardened material, and a black matrix is ​​formed using the hardened material. For example, a method is as follows: the photosensitive resin composition of the present invention is coated on a transparent substrate and dried, a photomask is placed on the dried sample, an image is exposed and developed through the photomask, and thermal curing or photocuring is performed as needed, thereby forming a black matrix.

[0232] (3) The formation of the black matrix (3-1) Coating of the photosensitive resin composition The photosensitive resin composition for black matrix coating can be applied to a transparent substrate using methods such as spin coating, wire rod coating, flow coating, die coating, roller coating, or spray coating. Among these methods, die coating is superior because it significantly reduces the amount of coating liquid used, completely eliminates the effects of mist that occurs with spin coating, and suppresses the formation of foreign matter.

[0233] The coating thickness, measured after drying, is typically preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and even more preferably in the range of 1 to 4 μm. Setting the coating thickness below the aforementioned upper limit tends to facilitate pattern development and gap adjustment during the liquid crystal unitization step. Setting the coating thickness above the aforementioned lower limit tends to facilitate achieving the desired color reproduction.

[0234] (3-2) Drying of the coating The drying of the coating film after the photosensitive resin composition is applied to the substrate is preferably performed using a drying method with a heated plate, an IR (Infrared) oven, or a convection oven. The drying conditions can be appropriately selected based on the type of solvent components and the performance of the dryer used. The drying time, depending on the type of solvent components and the performance of the dryer used, is typically selected within the range of 15 seconds to 5 minutes at a temperature of 40–200°C, and preferably within the range of 30 seconds to 3 minutes at a temperature of 50–130°C.

[0235] The higher the drying temperature, the better the adhesion of the coating to the transparent substrate. However, if the temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and resulting in poor development. Furthermore, the drying process of the coating can also be a vacuum drying method, which involves drying in a vacuum chamber without increasing the temperature.

[0236] (3-3) Exposure Image exposure is performed as follows: a negative mask pattern is superimposed on a coating of a photosensitive resin composition, and light of wavelengths from the ultraviolet to the visible light region is irradiated through the mask pattern. To prevent a decrease in sensitivity of the photopolymerizable layer caused by oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating before exposure, if necessary. The light source used in the above image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, etc. When used to irradiate light of a specific wavelength, optical filters may also be used.

[0237] (3-4) Development The black matrix of the present invention can be produced by the following method: after exposing a coating film formed of a photosensitive resin composition to an image using the aforementioned light source, developing it with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound, thereby forming an image on a substrate to produce a black matrix. The aqueous solution may further contain organic solvents, buffers, chelating agents, dyes, or pigments.

[0238] Examples of basic compounds include: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, and other inorganic basic compounds; or monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethylenediamine, ethylenediimide, tetramethylammonium hydroxide (TMAH), choline, and other organic basic compounds. These basic compounds can be used alone or in mixtures of two or more.

[0239] Examples of surfactants include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0240] Examples of organic solvents include isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used alone or in combination with aqueous solutions. There are no particular restrictions on the conditions for development. Generally, the development temperature is in the range of 10~50℃, with 15~45℃ being the most preferred and 20~40℃ being the most ideal. The development method can be any of the following: immersion development, jet development, brush development, or ultrasonic development.

[0241] (3-5) Heat curing treatment The developed substrate is subjected to either heat curing or photocuring, with heat curing being preferred. The heat curing conditions are as follows: temperature in the range of 100~280℃, preferably in the range of 150~250℃, and time in the range of 5~60 minutes. The height of the black matrix formed in the above manner is typically 0.5~5 μm, preferably 0.8~4 μm. Furthermore, the optical density (OD) per 1 μm thickness is 2.0 or higher, preferably 2.5 or higher, more preferably 3.0 or higher, and even more preferably 3.2 or higher.

[0242] [Formation of other color filters] Using the same process as described in (3-1) to (3-5) above, a photosensitive resin composition containing one of the colors red, green, and blue pigments is coated onto a transparent substrate with a black matrix. After drying, a photomask is stacked on the coating. The image is exposed and developed through the photomask, and thermal or photocuring is performed as needed to form a pixel image, thereby creating a color layer. This operation is performed separately on the photosensitive resin compositions of the three colors: red, green, and blue, thereby forming a color filter. The order of these operations is not limited to those described above.

[0243] [Colored spacer] The photosensitive resin composition obtained by the manufacturing method of the present invention can be used as a photoresist for colored spacers, in addition to the black matrix. When spacers are used in TFT-type LCDs (liquid crystal displays), malfunctions sometimes occur in the TFTs, which are switching elements, due to incident light. Colored spacers are used to prevent this; for example, Japanese Patent Application Publication No. 8-234212 discloses a method that makes the spacers light-shielding. Colored spacers can be formed using the same method as the black matrix, except when using a mask for colored spacers.

[0244] (3-6) Formation of transparent electrodes Color filters can have transparent electrodes such as ITO formed on the image in their original state, serving as a component in color displays, liquid crystal displays, etc. However, to improve surface smoothness or durability, a surface coating such as polyamide or polyimide can also be applied to the image as needed. Furthermore, in some applications such as planar alignment type drive (IPS mode), there are cases where transparent electrodes are not formed.

[0245] [Block] The photosensitive resin composition obtained by the manufacturing method of the present invention, or the photosensitive resin composition of the present invention, can also be used to form spacers, especially spacers for dividing the organic layers of an organic electroluminescent element. Examples of organic layers used in organic electroluminescent elements include, for example, the organic layers used in hole injection layers, hole transport layers, or hole transport layers on hole injection layers as described in Japanese Patent Application Publication No. 2016-165396.

[0246] Regarding the use of a spacer wall made from a photosensitive resin composition obtained by the manufacturing method of the present invention or a photosensitive resin composition of the present invention, the manufacturing method will be described accordingly.

[0247] (4-1) Support The same support and substrate used to form the spacer walls can be used as the support and substrate used to form the black matrix described above.

[0248] (4-2) Spacer The following description, regarding its use as a spacer, will be based on specific examples of a method for forming a spacer using a photosensitive resin composition obtained by the manufacturing method of the present invention or a photosensitive resin composition of the present invention.

[0249] Typically, a photosensitive resin composition is applied to the substrate to which spacers are to be formed, in a film or pattern, by means of coating or other methods, and the solvent is allowed to dry. Subsequently, a pattern is formed by methods such as photolithography with exposure and development. Afterward, additional exposure or heat curing is performed as needed to form spacers on the substrate.

[0250] (4-3) Formation of the partition wall In the method of forming the spacers of the photosensitive resin composition obtained by the manufacturing method of the present invention or the photosensitive resin composition of the present invention, the specific methods of supplying the photosensitive resin composition to the substrate, the drying method, the exposure method, the development method, the additional exposure and the thermosetting treatment can be the same as those used in the formation of the black matrix described above.

[0251] When used as a spacer, its size or shape is adjusted according to the specifications of the organic electroluminescent element to which it is applied, and the height of the spacer formed by the photosensitive resin composition is usually about 0.5 to 10 μm.

[0252] [Organic electroluminescent element] The organic electroluminescent element of the present invention comprises a hardened material, such as a spacer wall, obtained by the manufacturing method of the present invention. For example, various organic electroluminescent devices can be manufactured using a substrate with a spacer pattern produced by the above method. There are no particular limitations on the method for forming the organic electroluminescent device, but it is preferable to manufacture the organic electroluminescent device by forming a spacer pattern on the substrate using the above method, and then forming an organic layer such as a pixel by a wet process such as vapor deposition, casting, spin coating, or inkjet printing, whereby a functional material is sublimated and attached to the area surrounded by the spacers on the substrate under vacuum.

[0253] Examples of organic electroluminescent elements include bottom-emitting type and top-emitting type. As a bottom-emitting type, it is fabricated, for example, by forming spacers on a glass substrate with stacked transparent electrodes, and stacking a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in the opening surrounded by the spacers. On the other hand, as a top-emitting type, it is fabricated, for example, by forming spacers on a glass substrate with stacked metal electrode layers, and stacking an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in the opening surrounded by the spacers. Examples of light-emitting layers include organic electroluminescent layers described in Japanese Patent Application Publication No. 2009-146691 or Japanese Patent Publication No. 5734681. Alternatively, quantum dots described in Japanese Patent Publication No. 5653387 or Japanese Patent Publication No. 5653101 may be used.

[0254] The layer composition is not limited to this. From the perspective of luminous efficiency, for example, each layer of the hole transport layer and electron transport layer can be composed of two or more layers. The thickness of each layer is not particularly limited, but from the perspective of luminous efficiency or brightness, it is usually 1~500 nm.

[0255] Organic light-emitting diodes (OLEDs) can form RGB colors separately in each opening, or multiple colors can be layered in a single opening. From the perspective of improving reliability, OLEDs can incorporate a sealing layer. This sealing layer functions to prevent moisture from the air from being absorbed into the OLED, thus preventing a decrease in luminous efficiency. From the perspective of improving light extraction efficiency, OLEDs can incorporate a low-reflection film at the air-to-air interface. By placing a low-reflection film at the air-to-element interface, it is expected to reduce the refractive index difference and suppress reflection at the interface. Such low-reflection films can utilize technologies such as moth-eye structures and multilayer films.

[0256] When organic light-emitting elements are used as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of a certain pixel from leaking into other pixels. Furthermore, when the electrodes are made of metal, it is necessary to prevent the image quality from degrading due to the reflection of external light. Therefore, it is preferable to give the spacers constituting the organic light-emitting elements light-shielding properties. In organic electroluminescent devices, electrodes must be provided above and below the spacer walls. Therefore, from the viewpoint of insulation, the spacer walls are preferably high in resistance and low in dielectric constant. Thus, when a colorant is used to impart light-shielding properties to the spacer walls, the aforementioned organic pigments with high resistance and low dielectric constant are preferred.

[0257] [Image display device] The manufacturing method of the image display device of the present invention is characterized by using a hardened material obtained by the manufacturing method of the present invention, or a black matrix obtained by the manufacturing method of the present invention. Furthermore, the image display device of the present invention includes a hardened object obtained by the manufacturing method of the present invention, or a black matrix obtained by the manufacturing method of the present invention. The image display device of the present invention includes a hardened object formed by curing the photosensitive resin composition of the present invention. Examples of manufacturing methods for this device include: methods for manufacturing hardened objects, black matrices, or spacers formed using the photosensitive resin composition obtained by the manufacturing method of the present invention or the photosensitive resin composition of the present invention. As an image display device of the present invention, it is not particularly limited as long as it is a device for displaying images or videos, and examples include liquid crystal display devices or organic EL displays.

[0258] Liquid crystal display device The liquid crystal display device of the present invention is one that has the black matrix of the present invention, and the formation order or formation position of the color pixels or the black matrix is ​​not particularly limited.

[0259] Liquid crystal display devices are typically manufactured as follows: an alignment film is formed on a color filter; spacers are distributed on the alignment film; and the film is then bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell, and it is connected to a counter electrode. The alignment film is preferably a resin film such as polyimide. The alignment film is typically formed using gravure printing and / or flexible printing, and its thickness is tens of nanometers. After curing the alignment film by thermal baking, a surface treatment is performed by ultraviolet irradiation or by using a rubbing cloth to achieve a surface condition that allows for adjustment of the liquid crystal slope.

[0260] As spacers, spacers with sizes corresponding to the gap (void) with the opposing substrate are used, typically preferably 2~8 μm. Alternatively, photosensitive spacers (PS) formed on a color filter substrate using photolithography can be used instead of spacers. As the opposing substrate, an array substrate is typically used, preferably a TFT (thin-film transistor) substrate.

[0261] The bonding gap between the liquid crystal display (LCD) cell and the opposing substrate varies depending on the application of the LCD device, and is typically selected within the range of 2 to 8 μm. After bonding with the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV (ultraviolet) irradiation and / or heating, thereby sealing the periphery of the liquid crystal cell. After the sealed liquid crystal cells are cut into panel units, the pressure is reduced in a vacuum chamber. The liquid crystal injection port is then immersed in liquid crystal, and liquid crystal is injected into the liquid crystal cells through leakage into the chamber. The pressure reduction in the liquid crystal cells is typically 1×10⁻² to 1×10⁻⁷ Pa, preferably 1×10⁻³ to 1×10⁻⁶ Pa. Furthermore, it is preferable to heat the liquid crystal cells during pressure reduction, typically at 30 to 100°C, more preferably at 50 to 90°C. The heating during pressure reduction is typically maintained for 10 to 60 minutes, after which the cells are immersed in liquid crystal. UV-curable resin is then cured to seal the liquid crystal injection port of the liquid crystal cells, thereby manufacturing a liquid crystal display device (panel).

[0262] There are no particular restrictions on the type of liquid crystal; it can be any of the previously known liquid crystals, such as aromatic, aliphatic, or polycyclic compounds, including lyotropic and thermotropic liquid crystals. Thermotropic liquid crystals include, for example, nematic, smectic, and cholesteric liquid crystals, and can be any of these types.

[0263] [Organic EL Display] The organic EL display of the present invention is manufactured using the color filter of the present invention or the organic electroluminescent element of the present invention.

[0264] When using the color filter of the present invention to fabricate an organic EL display, for example as shown in FIG1, a pattern formed by a photosensitive resin composition (i.e., pixels 20 and a resin black matrix (not shown) disposed between adjacent pixels 20) is first formed on a transparent support substrate 10 to fabricate a color filter. An organic light emitter 500 is then deposited on the color filter, separating an organic protective layer 30 and an inorganic oxide film 40, thereby fabricating an organic EL element 100. Furthermore, at least one of the pixels 20 and the resin black matrix is ​​fabricated using the photosensitive resin composition of the present invention. Examples of methods for depositing the organic light emitter 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 above the color filter; or bonding an organic light emitter 500 formed on another substrate to the inorganic oxide film 40. An organic EL display can be made using the organic EL element 100 made in this way, for example, by the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, written by Shizushi Tokito, Chinatsu Adachi, and Hideyuki Murata).

[0265] Furthermore, the color filter of the present invention can be applied to both passively driven organic EL displays and actively driven organic EL displays.

[0266] Methods for controlling the molecular weight of resins containing carboxyl groups The method for controlling the molecular weight of a carboxyl-containing resin of the present invention comprises: 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, thereby obtaining a second reaction product A containing liquid; adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second reaction product A containing liquid and reacting them to obtain a carboxyl-containing resin. In detail, it is the same as step B and step C in the method for manufacturing a carboxyl-containing resin of the present invention.

[0267] When obtaining a resin containing carboxyl groups, a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) can be added to the liquid containing the second reaction product A and reacted. The preferred types or preferred amounts of epoxy compounds (a), unsaturated monocarboxylic acids (b), polycarboxylic acid dianhydrides (c), polycarboxylic acid monohydrides (d), and polyols (e) are the same as those described above in the manufacturing method of resins containing carboxyl groups. As the organic solvent used in the reaction to obtain the first reaction product A containing liquid, the organic solvent used in the method for manufacturing the carboxyl-containing resin of the present invention can preferably be used. [Example]

[0268] The invention is illustrated in more detail by way of examples, but the invention is not limited to the following examples as long as it does not deviate from its spirit.

[0269] <Examples 1-4: Synthesis of resins (1)-(4) containing carboxyl groups>

[0270] [Chemistry 27]

[0271] 265 g of the epoxy compound with the above structure (epoxy equivalent 240), 80 g of acrylic acid, 350 g of propylene glycol monomethyl ether acetate (PGMEA), 4 g of triphenylphosphine, and 0.3 g of p-methoxyphenol were added to a flask equipped with a thermometer, stirrer, and condenser. The mixture was stirred and reacted at 100°C until the acid value became below 5 mgKOH / g. The reaction took 9 hours, yielding a liquid containing the first reaction product A, which contained the intermediate. After cooling the obtained liquid containing the first reaction product A to 50°C, the water content was measured using a Karl von Somdej moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd., MKA-610). Water was added while stirring the liquid containing the first reaction product A at 50°C to control the water content of the liquid containing the reaction product A in a manner that is as recorded in Table 1. The second reaction product A containing liquid with controlled moisture content, 10 g of trimethylolpropane (TMP), 112 g of biphenyltetracarboxylic acid 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. The mixture was stirred and reacted at 105°C for 20 hours to obtain resin containing carboxyl groups (1) to (4). The weight-average molecular weight (Mw) of polystyrene containing carboxyl groups obtained by GPC (Waters Corporation, 2695) is converted and recorded in Table 1.

[0272] [Table 1] Example 1 2 3 4 Resins containing carboxyl groups (1) (2) (3) (4) Water content of intermediate solution [quality%] 0.10 0.20 0.30 0.45 Mw 9800 7900 7200 4800

[0273] According to Examples 1-4 shown in Table 1, it can be seen that by having a step to control the water content of the liquid containing reaction product A, the weight average molecular weight of the resin containing carboxyl groups can be controlled. Thus, according to the manufacturing method of the present invention, the molecular weight of the resin containing carboxyl groups can be controlled, and the performance stability of the resin containing carboxyl groups between manufacturing batches can be maintained.

[0274] 10: Transparent support substrate 20 pixels 30: Organic protective layer 40: Inorganic oxide film 50: Transparent Anode 51: Hole Injection Layer 52: Hole Transport Layer 53: Emissive Layer 54: Electron Injection Layer 55: Cathode 100: Organic EL element 500: Organic light-emitting body

Claims

1. A method for manufacturing a carboxyl-containing resin, comprising the following steps: Step A, reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent to obtain a first reaction product A containing liquid; Step B, controlling the water content of the first reaction product A containing liquid by adding water to the first reaction product A containing liquid to obtain a second reaction product A containing liquid; and Step C, adding a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) to the second reaction product A containing liquid and reacting them to obtain a carboxyl-containing resin; wherein in 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 monohydric acid (d), the unsaturated monocarboxylic acid (b) contains an alkenyl carboxylic acid, and the polybasic acid dianhydride (c) is a compound represented by general formula (c1). The aforementioned polybasic acid monohydric anhydride (d) contains any one of maleic anhydride, succinic anhydride, isocrine anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, and trimellitic anhydride. The aforementioned polyol (e) contains any one of trimethylolpropane, pentaerythritol, and dipentaerythritol. (In formula (c1), A is derived from the tetravalent organic group of the polybasic acid dianhydride).

2. The method for manufacturing a carboxyl-containing resin as claimed in claim 1, wherein water is added to the liquid containing the first reaction product A in such a way that the water content of the liquid containing the second reaction product A is 0.1% by mass or more and 0.5% by mass or less.

3. The method for manufacturing a resin containing a carboxyl group as claimed in claim 1, wherein the polyol (e) comprises trimethylolpropane.

4. A method for manufacturing a carboxyl-containing resin as claimed in any of claims 1 to 3, wherein the aforementioned polybasic acid dianhydride (c) comprises biphenyltetracarboxylic acid dianhydride.

5. A method for manufacturing a carboxyl-containing resin as claimed in any of claims 1 to 3, wherein the aforementioned polybasic acid monohydric anhydride (d) comprises tetrahydrophthalic anhydride.

6. A method for manufacturing an ink comprising (A) an alkali-soluble resin, an organic solvent, and (D) a pigment, and comprising: using a carboxyl-containing resin manufactured by any one of claims 1 to 5 as the aforementioned (A) alkali-soluble resin.

7. A method for manufacturing a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and comprising: adjusting a carboxyl-containing resin manufactured by any one of claims 1 to 5 as the aforementioned (A) alkali-soluble resin.

8. A method for manufacturing the photosensitive resin composition of claim 7, wherein the photosensitive resin composition further contains (D) a colorant.

9. A method for manufacturing a hardened material, comprising: hardening a photosensitive resin composition obtained using the manufacturing method of claim 7 or 8.

10. A method for manufacturing a black matrix, comprising: forming a black matrix using a hardened material obtained by the manufacturing method of claim 9.

11. A method for manufacturing an image display device, characterized in that: it uses a hardened material obtained by the manufacturing method of claim 9 or a black matrix obtained by the manufacturing method of claim 10.

12. A method for controlling the molecular weight of a resin containing a carboxyl group, comprising: controlling the water content of a first reaction product A containing liquid obtained by reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent, thereby obtaining a second reaction product A containing liquid; adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second reaction product A containing liquid and reacting them to obtain a resin containing a carboxyl group, wherein the unsaturated monocarboxylic acid (b) contains an alkenyl carboxylic acid, the polybasic acid dianhydride (c) is a compound represented by general formula (c1), and the polybasic acid monohydric acid (d) contains any one of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl terephthalic anhydride, terephthalic anhydride, trimellitic anhydride, (in formula (c1), A is derived from a tetravalent organic group of a polybasic acid dianhydride).

13. The method for controlling the molecular weight of the carboxyl-containing resin as claimed in claim 12, 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 such that the water content of the solution containing the second reaction product A is 0.1% by mass or more and 0.5% by mass or less, thereby obtaining the second reaction product A containing liquid.

14. The method for controlling the molecular weight of the carboxyl-containing resin as claimed in claim 12, wherein the carboxyl-containing resin is obtained by adding a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) to the liquid containing the second reaction product A and reacting them, wherein the polyol (e) contains any one of trimethylolpropane, pentaerythritol, and dipentaerythritol.

15. The method for controlling the molecular weight of the carboxyl-containing resin as claimed in claim 13, wherein the carboxyl-containing resin is obtained by adding a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) to the liquid containing the second reaction product A and reacting them, wherein the polyol (e) contains any one of trimethylolpropane, pentaerythritol, and dipentaerythritol.

16. The method for controlling the molecular weight of a carboxyl-containing resin as claimed in claim 14, wherein the polyol (e) comprises trimethylolpropane.

17. The method for controlling the molecular weight of a carboxyl-containing resin as claimed in claim 15, wherein the polyol (e) comprises trimethylolpropane.

18. A method for controlling the molecular weight of a carboxyl-containing resin as claimed in any of claims 12 to 17, wherein the aforementioned polybasic acid dianhydride (c) comprises biphenyltetracarboxylic acid dianhydride.

19. A method for controlling the molecular weight of a carboxyl-containing resin as claimed in any of claims 12 to 17, wherein the aforementioned polybasic acid monohydric anhydride (d) comprises tetrahydrophthalic anhydride.

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