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

Abstract

Provided are a method for producing a carboxyl group-containing resin having excellent performance stability between production lots and excellent controllability of molecular weight, and a method for controlling the molecular weight of a carboxyl group-containing resin. The method for producing a carboxyl group-containing resin of the present 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 and reacting a polybasic acid dianhydride (c) and a polybasic acid monoanhydride (d) to the second reaction product A-containing liquid to obtain a carboxyl group-containing resin.

Description

Technical Field

[0001] This invention relates to a method for manufacturing carboxyl-containing resins, a method for manufacturing inks, a method for manufacturing photosensitive resin compositions, a method for manufacturing cured products, a method for manufacturing black matrices, a method for manufacturing image display devices, and a method for controlling the molecular weight of carboxyl-containing resins.

[0002] This application claims priority to Japanese Patent Application No. 2020-182984, filed in Japan on October 30, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Color filters are typically obtained as follows: a black matrix is ​​formed on the surface of a transparent substrate such as glass or plastic. Then, pixels of three or more different colors, such as red, green, and blue, are sequentially formed in a grid, stripe, or mosaic pattern. The pattern size varies depending on the application of the color filter and the colors used, but is usually around 5–700 μm.

[0004] As a representative manufacturing method for color filters, photolithography using photosensitive resin compositions is currently known. In the case of manufacturing color filters using photolithography, firstly, a photosensitive resin composition containing a carboxyl-containing resin capable of alkaline development is coated onto a transparent substrate and dried. Next, an image is exposed, developed with an alkaline developer, and then cured at a high temperature above 200°C to form a pattern. However, the linewidth and film thickness of this photosensitive resin composition vary depending on the molecular weight and viscosity of the carboxyl-containing resin. Therefore, if the molecular weight difference between manufacturing batches of the carboxyl-containing resin is large, problems such as reduced color filter yield will occur.

[0005] Against this backdrop, a method is sought to stably control the molecular weight of carboxyl-containing resins during manufacturing. For example, Patent Documents 1 and 2 describe methods for manufacturing carboxyl-containing resins using specific conditions.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2000-336116

[0009] Patent Document 2: Japanese Patent Application Publication No. 2005-41958 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] The inventors manufactured carboxyl-containing resins using the manufacturing methods described in Patent Documents 1 and 2, and found that the molecular weight stability between manufacturing batches was insufficient.

[0012] Therefore, the object of the present invention is to provide a method for manufacturing a carboxyl-containing resin that can control molecular weight and exhibits excellent batch-to-batch performance stability, and a method for controlling the molecular weight of the carboxyl-containing resin.

[0013] Solution for solving the problem

[0014] In order to solve the aforementioned problems, the inventors conducted in-depth research and discovered that a specific method for manufacturing carboxyl-containing resins can solve these problems. Therefore, the main point of this invention is as follows.

[0015] [1] A method for manufacturing a carboxyl-containing resin, comprising the following steps:

[0016] Step A involves reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent to obtain a first liquid containing reaction product A.

[0017] Step B involves controlling the water content of the first liquid containing reaction product A to obtain a second liquid containing reaction product A; and...

[0018] Step C involves adding polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) to the aforementioned second liquid containing reaction product A and reacting them to obtain a carboxyl-containing resin.

[0019] [2] According to the method for manufacturing carboxyl-containing resin described in [1], the water content of the first liquid containing reaction product A is controlled by adding water to the liquid containing reaction product A, thereby obtaining the second liquid containing reaction product A.

[0020] [3] In the method for manufacturing the carboxyl-containing resin according to [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.

[0021] [4] The method for manufacturing a carboxyl-containing resin according to any one of [1] to [3], wherein in the aforementioned step C, a polyol (e) is further added and reacted.

[0022] [5] According to the method for manufacturing a carboxyl-containing resin described in [4], wherein the aforementioned polyol (e) comprises trimethylolpropane.

[0023] [6] The method for manufacturing a carboxyl-containing resin according to any one of [1] to [5], wherein the aforementioned polybasic acid dianhydride (c) comprises biphenyltetracarboxylic acid dianhydride.

[0024] [7] The method for manufacturing a carboxyl-containing resin according to any one of [1] to [6], wherein the aforementioned polybasic acid monohydric anhydride (d) comprises tetrahydrophthalic anhydride.

[0025] [8] A method for manufacturing ink, wherein the ink comprises (A) an alkali-soluble resin, an organic solvent, and (D) a pigment.

[0026] The manufacturing method includes the following steps: mixing a carboxyl-containing resin manufactured by any one of the manufacturing methods in [1] to [7] as the aforementioned (A) alkali-soluble resin.

[0027] [9] A method for manufacturing a photosensitive resin composition, wherein the photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator.

[0028] The manufacturing method includes the following steps: mixing a carboxyl-containing resin manufactured by any one of the manufacturing methods in [1] to [7] as the aforementioned (A) alkali-soluble resin.

[0029]

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

[0030]

[11] A method for manufacturing a cured material, comprising the step of curing a photosensitive resin composition obtained by the manufacturing method described in [9] or

[10] .

[0031]

[12] A method for manufacturing a black matrix, comprising the steps of forming a black matrix using a cured material obtained by the manufacturing method described in

[11] .

[0032]

[13] A method for manufacturing an image display device, characterized in that a cured material obtained by the manufacturing method described in

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

[12] is used.

[0033]

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

[0034]

[15] According to the method for controlling the molecular weight of the carboxyl-containing resin described in

[14] , water is added to the liquid containing the first reaction product A in such a way that the water content of the solution containing the liquid containing the second reaction product A is 0.1% by mass or more and 0.5% by mass or less, and the water content of the liquid containing the first reaction product A is controlled to obtain the liquid containing the second reaction product A.

[0035]

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

[14] or

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

[0036]

[17] According to the method for controlling the molecular weight of the carboxyl-containing resin described in

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

[0037]

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

[14] to

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

[0038]

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

[14] to

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

[0039] The effects of the invention

[0040] According to the present invention, a method for manufacturing a carboxyl-containing resin that can control molecular weight and exhibits excellent batch-to-batch performance stability, and a method for controlling the molecular weight of the carboxyl-containing resin can be provided. Attached Figure Description

[0041] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an organic EL element equipped with the color filter of the present invention. Detailed Implementation

[0042] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented by various modifications within the scope of its spirit.

[0043] It should be noted that in this invention, "(meth)acrylic acid" refers to "acrylic acid and / or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

[0044] 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 later.

[0045] In this invention, "photosensitive resin composition" is sometimes referred to as "resin".

[0046] In this invention, weight-average molecular weight refers to the weight-average molecular weight (Mw) of polystyrene obtained by gel permeation chromatography (GPC).

[0047] In this invention, "amine value" refers to the amine value converted from the effective solid component unless otherwise specified, and is expressed as the mass of KOH equal to the amount of alkali per 1g of the dispersant solid component. It should be noted that the determination method is described below.

[0048] [Manufacturing method of carboxyl-containing resin]

[0049] The method for manufacturing the carboxyl-containing resin of the present 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 liquid containing reaction product A; Step B, controlling the water content of the first liquid containing reaction product A obtained in Step A to obtain a second liquid containing reaction product A; and Step C, adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the second liquid containing reaction product A obtained in Step B and reacting them to obtain the carboxyl-containing resin.

[0050] The reaction product A contained in the first liquid containing reaction product A obtained in step A can also be referred to as an intermediate containing carboxyl resin, and therefore, it will sometimes be referred to as an "intermediate" below. Similarly, the reaction product A contained in the second liquid containing reaction product A obtained in step B will also sometimes be referred to as an "intermediate".

[0051] The liquid containing the first liquid containing reaction product A and the liquid containing the second liquid containing reaction product A can be any liquid mixture containing reaction product A, and can be a suspension, dispersion or solution, preferably a solution containing reaction product A.

[0052] <Process A>

[0053] Step A is a step in which an epoxy compound (a) is reacted with an unsaturated monobasic acid (b) in an organic solvent to synthesize reaction product A (intermediate) and obtain a first liquid containing reaction product A.

[0054] As for epoxy compounds (a), there are no particular limitations as long as they are compounds containing epoxy groups. For example, suitable options include: bisphenol A type epoxy resins (e.g., "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), 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., "jER807", "EP-4001", "EP..." manufactured by Mitsubishi Chemical Corporation). Epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., NER-7406 manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66℃)), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), phenolic varnish type epoxy resin (e.g., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EP-152 and EP-154 manufactured by Mitsubishi Chemical Co., Ltd., Dow Chemical Company's "DEN-438", (ortho, meta, para) cresol phenolic varnish epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., Nissan Chemical Co., Ltd.'s "TEPIC"), triphenol methane type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resins (Daicel Corporation's "CELLOXIDE 2021P", "CELLOXIDE..."). EHPE”), epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (e.g., “EXA-7200” manufactured by DIC Corporation and “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), copolymers of epoxy-containing (meth)acrylates with other free radical polymerizable monomers, and epoxy compounds represented by the following general formulas (a1) to (a6).

[0055] Specifically, for example, as an epoxy compound represented by the following general formula (a1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. can be cited; as an epoxy compound represented by the following general formula (a2), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. can be cited; 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.

[0056]

[0057] In the above general formula (a1), b11 represents the average value, which is a number from 0 to 10. R 11 It can represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, phenyl groups, naphthyl groups, or biphenyl groups.

[0058] It should be noted that multiple Rs exist in one molecule 11 Choose whether they are the same or different from each other.

[0059]

[0060] In the above general formula (a2), b12 represents the average value, which is a number from 0 to 10. R 21 It can represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, phenyl groups, naphthyl groups, or biphenyl groups.

[0061] It should be noted that multiple Rs exist in one molecule 21 Choose whether they are the same or different from each other.

[0062]

[0063] In the above general formula (a3), X represents the linking group shown in the following general formulas (a3-1) or (a3-2). The molecular structure contains more than one adamantane structure. b13 represents an integer of 2 or 3.

[0064] Of these, from the viewpoint of the patterning properties of resin, X is preferred (a3-1), and b13 is preferred (2).

[0065]

[0066] In the above general formulas (a3-1) and (a3-2), R 31 ~R 34 and R 35 ~R 37 Each of these can independently represent an adamantyl group, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms having a substituent, or a phenyl group having a substituent. Additionally, * in the formula represents a bonding site in formula (a3).

[0067] As formula (a3-1), from the viewpoint of the patterning properties of the resin, it is preferable to have two adamantyl alkyl groups and one hydrogen atom. As formula (3a-2), from the viewpoint of the anti-corrosion patterning properties, it is preferable to have two adamantyl alkyl groups and one hydrogen atom.

[0068]

[0069] In the above general formula (a4), p and q each independently represent integers from 0 to 4, and R 41 and R 42 Each of the following independently represents an alkyl or halogen atom having 1 to 20 carbon atoms. R 43 and R 44 Each of the two groups independently represents an alkylene group having 1 to 5 carbon atoms. x and y independently represent integers greater than 0.

[0070] Of these, from the viewpoint of the patterning properties of the resin, p, q, x, and y are preferably 0.

[0071]

[0072] In the above general formula (a5), R 51 ~R 54 Each is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 55 R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. 56 Each is an alkylene group having 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 integer from 0 to 5.

[0073] Among these, from the perspective of the patterning properties of resin, R 51 ~R 54 Hydrogen atoms are preferred, k is preferably 2, and l and m are preferably 0.

[0074]

[0075] In the above general formula (a6), n and o are each an independent integer from 1 to 9.

[0076] R 23 This indicates 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. It should be noted that multiple R atoms present in one molecule... 23 Choose whether they are the same or different from each other.

[0077] From the viewpoint of resin patterning properties, epoxy compounds represented by any of the general formulas (a1) to (a6) are preferred, epoxy compounds represented by (a3), (a4), or (a5) are more preferred, and epoxy compounds represented by (a5) are even more preferred.

[0078] An unsaturated monocarboxylic acid (b) is any compound that has only one acid group and one or more free radical polymerizable unsaturated bonds in one molecule, and the carboxyl group is preferred as the acid group.

[0079] By reacting an epoxide (a) with an unsaturated monocarboxylic acid (b) in an organic solvent, thereby reacting the acid group with the epoxy group of the epoxide, a first liquid containing a reaction product A, which is an intermediate in which a free radical polymerizable double bond has been introduced into the epoxide, can be obtained.

[0080] Examples of unsaturated monocarboxylic acids (b) include: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substituents of (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2- (Methacryloxybutylsuccinic acid), 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone added to (meth)acrylic acid, monomers having one carboxyl group at the end, monomers such as hydroxyalkyl esters of (meth)acrylic acid having one hydroxyl group at the end, acids such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) added to compounds such as pentaerythritol tri(meth)acrylic acid esters having one or more olefinic unsaturated groups and one carboxyl group at the end, and (meth)acrylic acid dimers.

[0081] From the viewpoint of resin sensitivity and stability over time, alkenyl carboxylic acid is preferred as an unsaturated monocarboxylic acid (b), and (meth)acrylic acid is more preferred.

[0082] As organic solvents, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionic acid, 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.

[0083] As a method for reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent to obtain an intermediate, known techniques 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 50–150 °C.

[0084] As catalysts, tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used. Among these, from the viewpoint of reaction yield, tertiary phosphine is preferred, and triphenylphosphine is more preferred.

[0085] As polymerization inhibitors, hydroquinone, methylhydroquinone, trimethylhydroquinone, p-methoxyphenol, and 2,6-di-tert-butyl-4-cresol can be used, for example. Among these, p-methoxyphenol and 2,6-di-tert-butyl-4-cresol are preferred from the viewpoint of reaction yield and resin sensitivity, and p-methoxyphenol is more preferred.

[0086] It should be noted that the epoxy compound (a), the unsaturated monocarboxylic acid (b), the organic solvent, the catalyst, and the polymerization inhibitor can all be used individually or in combination with two or more.

[0087] The amount of unsaturated monocarboxylic acid (b) relative to the epoxy group equivalent 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 residual epoxy content is reduced, and the tendency to gelation during the reaction with the polycarboxylic anhydride in step A can be suppressed. In addition, 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.

[0088] <Process B>

[0089] Process B controls the moisture content of the first liquid containing reaction product A obtained in process A to obtain the second liquid containing reaction product A.

[0090] The method for manufacturing the carboxyl-containing resin of the present invention includes step B, thereby enabling control of the molecular weight of the carboxyl-containing resin.

[0091] There are no particular limitations on the method for controlling the water content of the first liquid containing reaction product A obtained in process A. For example, the following methods can be used: adding water to the first liquid containing reaction product A, or dehydrating the first liquid containing reaction product A.

[0092] When water is added to the first liquid containing reaction product A, it can be added alone or as a mixture of water and an organic solvent. Furthermore, the temperature of the first liquid containing reaction product A at the time of addition is preferably 20°C to 80°C, more preferably 30°C to 70°C, even more preferably 40°C to 60°C, and particularly preferably 45°C to 55°C. By setting the temperature within the aforementioned range, water can be uniformly dispersed and dissolved in the first liquid containing reaction product A.

[0093] The addition of water to the first liquid containing reaction product A is preferably carried out while stirring the first liquid containing reaction product A. This allows the water to be uniformly dispersed and dissolved in the first liquid containing reaction product A.

[0094] The amount of water added to the liquid containing the first reaction product A is preferably 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, even more preferably 0.1% by mass or more, and particularly preferably 0.18% by mass or more. Additionally, it is preferably 1% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.4% by mass or less. By setting the amount to the aforementioned lower limit or above, there is a tendency to reduce the residue of the photoresist. Furthermore, by setting the amount to the aforementioned upper limit or below, there is a tendency to improve the stability of the photoresist over time.

[0095] The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1% by mass is preferred, 0.03 to 0.8% by mass is more preferred, 0.06 to 0.6% by mass is even more preferred, 0.1 to 0.5% by mass is still preferred, and 0.18 to 0.4% by mass is particularly preferred.

[0096] Methods for dehydrating the liquid containing the first reaction product A include: drying using porous materials such as molecular sieves or silica gel, or dehydrating agents such as calcium chloride; and removing the water by vacuum distillation. From the viewpoint of the purity and yield of the carboxyl-containing resin, the method of removing the water by vacuum distillation is preferred.

[0097] When depressurization and distillation are performed, the pressure in the reaction vessel containing the first liquid containing reaction product A is preferably 70 kPa or less, more preferably 60 kPa or less, even more preferably 50 kPa or less, and particularly preferably 40 kPa or less.

[0098] In step B, from the viewpoint of reaction time, it is preferable to include the following step: by adding water to the first liquid containing reaction product A obtained in step A, the water content of the first liquid containing reaction product A is controlled, thereby obtaining a second liquid containing reaction product A.

[0099] The water content of the liquid containing reaction product A can be calculated using the Karl Fischer method as described in JIS K0113 (2005). Various moisture meters can be used, such as the KMA-610 manufactured by Kyoto Electronics Industry Co., Ltd.

[0100] <Process C>

[0101] Step C is a process in which polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) are added to the second liquid containing reaction product A obtained in step B and reacted to obtain a carboxyl-containing resin.

[0102] As for the dianhydride (c), it is acceptable as long as it is a compound having only two anhydride groups in one molecule. From the viewpoint of the patterning properties of the resist, compounds containing the general formula (c1) are preferred.

[0103]

[0104] In the above formula (c1), A is a tetravalent organic group derived from the dianhydride of a polybasic acid.

[0105] As the polybasic acid dianhydride (c) represented by general formula (c1), for example, biphenyltetracarboxylic dianhydride (BPDA), dicyclohexyltetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenonetetracarboxylic dianhydride can be used. Among these, from the viewpoint of the patterning properties of the resin, biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride are preferred, and biphenyltetracarboxylic dianhydride (BPDA) is more preferred.

[0106] 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, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnorbornadiene anhydride, norbornadiene anhydride, and trimellitic anhydride. From the viewpoint of resin patterning properties, succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are preferred, with tetrahydrophthalic anhydride being more preferred.

[0107] Both polybasic acid dianhydrides (c) and polybasic acid monohydrides (d) can be used alone or in combination with two or more.

[0108] The reaction to synthesize a carboxyl-containing resin by adding polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) to a second liquid containing reaction product A can also be carried out using known methods. For example, polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) can be added to the second liquid containing reaction product A, and the reaction can be carried out at a temperature of 50–150°C.

[0109] When polybasic acid dianhydride (c) and polybasic acid monohydric acid (d) are added to the second liquid containing reaction product A and reacted, polyol (e) can also be added and reacted further.

[0110] By further adding polyol (e) and reacting, a multi-branched structure can be introduced into the resulting carboxyl-containing resin, thereby improving the patterning properties of the resist.

[0111] As the polyol(e), for example, trimethylolpropane, pentaerythritol, and dipentaerythritol can be used. Among these, trimethylolpropane is preferred from the viewpoint of the patterning properties of the resist.

[0112] The amount of polyol (e) 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. Furthermore, it is preferably 1 equivalent or less, more preferably 0.9 equivalents or less, and even more preferably 0.8 equivalents or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve the stability of the resist over time; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to improve the sensitivity of the resist.

[0113] The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1 equivalent is preferred, 0.03 to 0.9 equivalent is more preferred, and 0.05 to 0.8 equivalent is even more preferred.

[0114] The amount of dianhydride (c) relative to one equivalent of the monohydric anhydride (d) of the polybasic acid 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 aforementioned lower limit or above, there is a tendency to improve the adhesion of the resist; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to reduce resist residue.

[0115] The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 50 equivalents is preferred, 0.3 to 30 equivalents is more preferred, and 0.5 to 10 equivalents is even more preferred.

[0116] The acid value of the carboxyl-containing resin manufactured by the method of the present invention is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, and particularly preferably 80 mg KOH / g or more. Furthermore, it is preferably 250 mg KOH / g or less, more preferably 200 mg KOH / g or less, further preferably 150 mg KOH / g or less, and particularly preferably 130 mg KOH / g or less. By setting it to the aforementioned lower limit or above, there is a tendency to reduce the residue of the photoresist. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to improve the adhesion of the photoresist.

[0117] The above upper and lower limits can be combined arbitrarily. For example, 10-250 mg KOH / g is preferred, 30-200 mg KOH / g is more preferred, 50-150 mg KOH / g is even more preferred, and 80-130 mg KOH / g is particularly preferred.

[0118] The weight-average molecular weight of the carboxyl-containing resin manufactured by the manufacturing method of the present invention is preferably 3,000 or more, more preferably 5,000 or more, further preferably 8,000 or more, and particularly preferably 12,000 or more. Furthermore, it is preferably 22,000 or less, more preferably 21,000 or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve the adhesion of the resist. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to reduce resist residue.

[0119] The above upper and lower limits can be combined arbitrarily. For example, 3000-22000 is preferred, 5000-22000 is more preferred, 8000-21000 is even more preferred, and 12000-21000 is particularly preferred.

[0120] [Liquids containing carboxyl-containing resins]

[0121] The liquid containing the carboxyl-containing resin obtained in step C contains the carboxyl-containing resin, an organic solvent, and water. The water content of the resulting liquid containing the carboxyl-containing resin is preferably 0.01% by mass or more and 1% by mass or less.

[0122] By keeping the moisture content within the aforementioned range, there is a tendency to reduce the residue of the resist using liquid containing carboxyl resin, and also to improve the long-term stability of the resist.

[0123] The water content of the liquid containing the carboxyl-containing resin 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, even more preferably 0.1% by mass or more, and particularly preferably 0.18% by mass or more. Furthermore, it is more preferably 0.8% by mass or less, further preferably 0.6% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.4% by mass or less. The above upper and lower limits can be combined arbitrarily; for example, 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 particularly preferably 0.18% by mass or more and 0.4% by mass or less is preferred. By setting it to the aforementioned lower limit or above, there is a tendency to reduce the residue of the resist using the aforementioned resin solution. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to improve the stability of the resist over time.

[0124] The carboxyl-containing resin contained in the liquid containing the carboxyl-containing resin is preferably a carboxyl-containing resin manufactured by the manufacturing method of the present invention.

[0125] The carboxyl-containing resin of the present invention preferably has a structure derived from epoxy compound (a).

[0126] The carboxyl-containing resin of the present invention preferably has a structure derived from an unsaturated monobasic acid (b).

[0127] The carboxyl-containing resin of the present invention preferably has a structure derived from the dianhydride (c) of the polybasic acid.

[0128] The carboxyl-containing resin of the present invention preferably has a structure derived from a polybasic acid monohydric anhydride (d).

[0129] The carboxyl-containing resin of the present invention preferably has a structure derived from polyol (e).

[0130] The preferred types and preferred mixing 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.

[0131] As the organic solvent contained in the liquid containing the carboxyl-containing resin, the organic solvent used in the method for manufacturing the carboxyl-containing resin of the present invention can preferably be used.

[0132] [Photosensitive Resin Composition]

[0133] The method for manufacturing the photosensitive resin composition of the present invention is a method for manufacturing a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. The manufacturing method includes the following steps: mixing a carboxyl-containing resin manufactured by the method of the present invention as (A) the alkali-soluble resin. It should be noted that the photosensitive resin composition manufactured by the method of the present invention may contain (D) a pigment.

[0134] <(A) Alkali-soluble resin>

[0135] The photosensitive resin composition of the present invention improves batch-to-batch performance stability by including a carboxyl-containing resin obtained in the manufacturing method of the present invention as (A) an alkali-soluble resin.

[0136] (A) Alkali-soluble resins may also contain other alkali-soluble resins.

[0137] 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 the coating obtained by coating the photosensitive resin composition and drying is exposed, the alkali-soluble resin having a carboxyl group is preferred. In addition, it is preferred to have an olefin unsaturated group, and it is even more preferred to have an alkali-soluble resin having both an olefin unsaturated group and a carboxyl group. Specifically, epoxy (meth)acrylate resins and acrylic copolymer resins having carboxyl groups can be cited as examples, and more specifically, the alkali-soluble resins described below as (A1-1), (A2-1), (A2-2), (A2-3), and (A2-4) can be cited as examples. One or more of them can be used. Of the above, epoxy (meth)acrylate resin (A1-1) having a carboxyl group is particularly preferred.

[0138] When manufacturing color filters, a polymer resin with acidic functional groups such as hydroxyl, carboxyl, phosphate, and sulfonic acid groups is used as the polymer resin to dissolve the non-exposed portion in the alkaline developer. From the viewpoint of solubility in the alkaline developer, a polymer resin with carboxyl groups is preferred. However, while phosphate and 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, sometimes leading to decreased storage stability.

[0139] Examples of epoxy (meth)acrylate resins having carboxyl groups include the following epoxy (meth)acrylate resin (A1-1).

[0140] <Epoxy (meth)acrylate resin (A1-1)>

[0141] An alkali-soluble resin is obtained by adding an unsaturated monocarboxylic acid to an epoxy compound and further reacting the monocarboxylic acid with an anhydride.

[0142] <Epoxy (meth)acrylate resin with carboxyl and olefinic unsaturated group bonds (A1-1)>

[0143] Epoxy compounds used as raw materials include, for example, bisphenol A type epoxy resins (e.g., "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), 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., "jER807", "EP-400", etc. manufactured by Mitsubishi Chemical Corporation). Epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., NER-7406 manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66℃)), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), phenolic varnish type epoxy resin (e.g., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EP-152 and EP-154 manufactured by Mitsubishi Chemical Co., Ltd., Dow Chemical Company's "DEN-438"), (ortho-, meta-, para-)cresol phenolic varnish epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., Nissan Chemical Co., Ltd.'s "TEPIC"), triphenol methane type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resins (Daicel Corporation's "CELLOXIDE 2021P", "CELLOXIDE..."). EHPE”), epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (e.g., “EXA-7200” manufactured by DIC Corporation, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins shown in the following general formulas (a1) to (a6).

[0144] Specifically, for example, as an epoxy resin represented by the following general formula (a1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. can be cited; as an epoxy resin represented by the following general formula (a2), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. can be cited; and as an epoxy resin represented by the following general formula (a4), "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. can be cited.

[0145]

[0146] In the above general formula (a1), b11 represents the average value, which is a number from 0 to 10. R 11 This indicates 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. It should be noted that multiple R atoms present in one molecule... 11 Choose whether they are the same or different from each other.

[0147]

[0148] In the above general formula (a2), b12 represents the average value, which is a number from 0 to 10. R 21 This indicates 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. It should be noted that multiple R atoms present in one molecule... 21 Choose whether they are the same or different from each other.

[0149]

[0150] In the above general formula (a3), X represents the linking group shown in the following general formulas (a3-1) or (a3-2). The molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0151]

[0152] In the above general formulas (a3-1) and (a3-2), R 31 ~R 34 and R 35 ~R 37 Each of these can independently represent an adamantyl group, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms having a substituent, or a phenyl group having a substituent. Additionally, * in the formula represents a bonding site in formula (a3).

[0153] As formula (a3-1), from the viewpoint of the patterning properties of the resin, it is preferable to have two adamantyl alkyl groups and one hydrogen atom. As formula (a3-2), from the viewpoint of the patterning properties of the resist, it is preferable to have two adamantyl alkyl groups and one hydrogen atom.

[0154]

[0155] In the above general formula (a4), p and q each independently represent integers from 0 to 4, and R 41 and R 42 Each of the following independently represents an alkyl or halogen atom having 1 to 20 carbon atoms. R 43 and R 44 Each of the two groups independently represents an alkylene group having 1 to 5 carbon atoms. x and y independently represent integers greater than 0.

[0156]

[0157] In the above general formula (a5), R 51 ~R 54 Each is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 55 R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. 56 Each is an alkylene group having 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 integer from 0 to 5.

[0158]

[0159] In the above general formula (a6), n and o are each an independent integer from 1 to 9.

[0160] R 23 This indicates 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. It should be noted that multiple R atoms present in one molecule... 23 Choose whether they are the same or different from each other.

[0161] Preferably, an epoxy compound represented by any one of the general formulas (a1), (a2) or (a6) is used.

[0162] Examples of unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substituents of (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, and 2- (Meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrogen phthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid.

[0163] Examples of (meth)acrylates include lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone added to (meth)acrylic acid; monomers having one hydroxyl group at the end; or monomers having one hydroxyl group at the end, such as hydroxyalkyl methacrylates; compounds having one hydroxyl group at the end, such as pentaerythritol trimeth)acrylates; acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) added to them; (meth)acrylates having one or more olefinic unsaturated groups and one carboxyl group at the end; and (meth)acrylic acid dimers.

[0164] From the perspective of sensitivity, (meth)acrylic acid is particularly preferred.

[0165] As a method for the addition reaction of unsaturated monocarboxylic acids, known techniques can be used. For example, the unsaturated monocarboxylic acid can be reacted with an epoxide at a temperature of 50–150 °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, benzyldimethylamine, and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0166] It should be noted that epoxides, unsaturated monocarboxylic acids, and catalysts can all be used individually or in combination of two or more.

[0167] The amount of unsaturated monocarboxylic acid used is preferably in the range of 0.5 to 1.2 equivalents relative to the epoxy group of the epoxy compound, and more preferably in the range of 0.7 to 1.1 equivalents.

[0168] By using an amount of unsaturated monocarboxylic acid above the aforementioned lower limit, the amount of unsaturated groups introduced becomes sufficient, and the subsequent reaction with the monocarboxylic acid monohydric anhydride becomes sufficient. In addition, there is a tendency to suppress the residual amount of epoxy groups. On the other hand, by setting the aforementioned amount below the aforementioned upper limit, there is a tendency to suppress the residual unsaturated monocarboxylic acid as unreacted material.

[0169] As a monohydric acid, examples include one or more monohydric acids 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.

[0170] The preferred anhydrides are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. The monoanhydride of tetrahydrophthalic acid is particularly preferred.

[0171] Regarding the addition reaction of a polybasic acid monohydric anhydride, a known method can also be used. Under the same conditions as the addition reaction of an unsaturated monobasic acid to an epoxy compound, the target product can be obtained by continuing the reaction. The amount of polybasic acid monohydric anhydride added is preferably such that the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g, and more preferably in the range of 20 to 140 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved alkali developability. Furthermore, by setting it to the upper limit or below, there is a tendency for improved curability.

[0172] The resulting epoxy (meth)acrylate resin (A1-1) typically has an acid value of 10 mg KOH / g or higher, preferably 50 mg KOH / g or higher, more preferably 80 mg KOH / g or higher, preferably 200 mg KOH / g or lower, and more preferably 150 mg KOH / g or lower. By setting the acid value to the aforementioned lower limit or higher, there is a tendency for improved developability. Furthermore, by setting the acid value to the aforementioned upper limit or lower, there is a tendency for improved alkali resistance.

[0173] The above upper and lower limits can be combined arbitrarily. For example, 10-200 mg KOH / g is preferred, 50-200 mg KOH / g is more preferred, and 80-150 mg KOH / g is even more preferred.

[0174] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (A1-1), as 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 particularly preferably 2500 or more. Furthermore, it is preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, even more preferably 8000 or less, and particularly preferably 7000 or less. By setting it to the aforementioned lower limit or above, there is a tendency for improved sensitivity, coating strength, and alkali resistance. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency for improved developability and resolubility.

[0175] The above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 1,500 to 10,000 is even more preferred, 2,000 to 8,000 is even more preferred, and 2,500 to 7,000 is particularly preferred.

[0176] <Acrylic copolymer resins (A2-1), (A2-2), (A2-3), (A2-4)>

[0177] As acrylic copolymer resins, various polymer compounds described in Japanese Patent Application Publication Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, 2003-233179, and 2007-270147 can be used. Resins of (A2-1) to (A2-4) are preferred, with resin (A2-1) being particularly preferred.

[0178] (A2-1): A resin obtained by adding at least a portion of the epoxy groups of an epoxy-containing (meth)acrylate to an unsaturated monocarboxylic acid, or by adding at least a portion of the hydroxyl groups generated by the addition reaction to a monocarboxylic acid anhydride.

[0179] (A2-2): A linear, alkali-soluble resin containing carboxyl groups in its main chain.

[0180] (A2-3): A resin in which an epoxy-containing unsaturated compound is added to the carboxyl group of the aforementioned (A2-2) resin.

[0181] (A2-4): (Meth)acrylic resin.

[0182] From the viewpoint of sensitivity, the photosensitive resin composition of the present invention further preferably includes at least one of (A1-1), (A2-1), and (A2-3) as an alkali-soluble resin containing olefinic unsaturated groups. From the viewpoint of surface curing properties, the photosensitive resin composition of the present invention particularly preferably includes (A1-1) as an epoxy (meth)acrylate resin as an alkali-soluble resin containing olefinic unsaturated groups.

[0183] (A) The proportion 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 particularly preferably 25% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency for the unexposed portion to have good solubility in the developer. In addition, by setting it to the aforementioned upper limit or below, excessive penetration of the developer into the exposed portion can be suppressed, and there is a tendency for the image sharpness and adhesion to be good.

[0184] The above upper and lower limits can be combined arbitrarily. For example, 5-90% by mass is preferred, 5-70% by mass is more preferred, 10-50% by mass is even more preferred, 10-30% by mass is still preferred, and 15-25% by mass is particularly preferred.

[0185] 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 include at least one of (A1-1), (A2-1), (A2-2), (A2-3) and (A2-4) mentioned above.

[0186] When the photosensitive resin composition of the present invention contains other alkali-soluble resins, the proportion thereof, from the viewpoint of resin patterning, is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of (A) alkali-soluble resins, or may not contain any of them.

[0187] <(B) Photopolymerizable monomers>

[0188] The photosensitive resin composition of the present invention contains (B) photopolymerizable monomers from the perspective of sensitivity and other aspects.

[0189] As (B) photopolymerizable monomers, examples include compounds having at least one olefinically unsaturated group within the molecule (hereinafter sometimes referred to as "olefinic monomers"). Specifically, examples include (meth)acrylic acid, alkyl (meth)acrylates, acrylonitrile, styrene, and esters of carboxylic acids with one olefinically unsaturated bond and polyols or monohydric alcohols.

[0190] As the (B) photopolymerizable monomer, a polyfunctional olefin monomer having two or more olefin unsaturated groups per molecule is particularly preferred. The number of olefin unsaturated groups in the polyfunctional olefin monomer is typically two or more, preferably three or more, more preferably four or more, further preferably five or more, particularly preferably six or more, and typically ten or less, preferably eight or less. By setting the value to the aforementioned lower limit or above, the photosensitive resin composition tends to become highly sensitive; conversely, by setting the value to the aforementioned upper limit or below, the curing shrinkage during polymerization tends to be smaller.

[0191] The above upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, 3 to 10 is more preferred, 4 to 10 is even more preferred, 5 to 8 is even more preferred, and 6 to 8 is particularly preferred.

[0192] Examples of polyfunctional olefin 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 and aromatic polyhydroxy compounds with unsaturated and polycarboxylic acids.

[0193] 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.; methacrylates obtained by replacing the acrylates of these example compounds with methacrylates; similarly, itaconic acid esters obtained by replacing them with itaconic acid esters; crotonic acid esters obtained by replacing them with crotonic acid esters; or maleic acid esters obtained by replacing them with maleic acid esters.

[0194] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and other acrylates and methacrylates of aromatic polyhydroxy compounds.

[0195] Esters, obtained through the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds, are not necessarily single substances. 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, isophthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0196] Furthermore, examples of the polyfunctional olefin monomers used in this invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates, such as those obtained by reacting a polyepoxide compound with a hydroxyl (meth)acrylate or an addition reaction product of (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate.

[0197] They can be used individually or in combination with two or more.

[0198] (B) The proportion of photopolymerizable monomer is not particularly limited, but 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, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition. By keeping the content of photopolymerizable monomer below the above-mentioned upper limit, the permeability of the developer to the exposed portion becomes moderate, and there is a tendency to obtain a good image. The content of photopolymerizable monomer (b) is generally 1% by mass or more, preferably 5% by mass or more. By keeping it above the above-mentioned lower limit, there is a tendency to improve UV-based photocuring and also improve alkaline developability.

[0199] The above upper and lower limits can be combined arbitrarily. For example, 1 to 90% by mass is preferred, 1 to 70% by mass is more preferred, 1 to 50% by mass is even more preferred, 5 to 30% by mass is even more preferred, 5 to 20% by mass is even more preferred, and 5 to 10% by mass is particularly preferred.

[0200] <(C) Photopolymerization Initiator>

[0201] The photosensitive resin composition of this invention contains (C) a photopolymerization initiator. A photopolymerization initiator is a component that directly absorbs light, induces a cleavage reaction or a hydrogen abstraction reaction, and generates polymerizable free radicals. Additives such as sensitizing pigments can be added as needed.

[0202] Examples of photopolymerization initiators include metallocene compounds containing dititanium compounds as described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated oxadiazole 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-aminoalkylphenyl ketone derivatives as described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0203] Examples of titanium diacene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,6-difluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,4-difluorophenyl-1-yl) titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl) titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl) titanium, and dicyclopentadienyl[2,6-di-fluoro-3-(pyrrole-1-yl)-phenyl-1-yl] titanium.

[0204] 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.

[0205] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6”-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0206] Examples of halomethyl-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-triazine.

[0207] Examples of α-aminoalkylphenyl ketone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopentylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminophenylmethylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0208] 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. Using alkali-soluble resins containing phenolic hydroxyl groups can sometimes be disadvantageous in terms of sensitivity.

[0209] Oxime ester compounds, as photopolymerization initiators, possess structures that absorb ultraviolet light, transmit light energy, and generate free radicals. Therefore, they are highly sensitive and thermally stable, allowing for the design of highly sensitive photosensitive resin compositions with minimal input. In particular, from the viewpoint of light absorption by i-rays (365 nm) from the exposure light source, oxime ester compounds containing optionally substituted carbazole groups (groups having optionally substituted carbazole rings) are more preferable as they better reflect their structural characteristics. Currently, the market demands high opacity, deep black matrices in films, and increasingly higher pigment concentrations. This makes them especially effective in such cases.

[0210] Examples of oxime ester compounds include compounds containing the structural moiety shown in the following general formula (22), and preferably oxime ester compounds shown in the following general formula (23).

[0211]

[0212] In the above equation (22), R 22The terms represent the substituted groups, which are alkylol groups with 2 to 12 carbon atoms, heteroarylalkylol groups with 1 to 20 carbon atoms, enoyl groups with 3 to 25 carbon atoms, cycloalkanol groups with 3 to 8 carbon atoms, alkoxycarbonylalkylol groups with 3 to 20 carbon atoms, phenoxycarbonylalkylol groups with 8 to 20 carbon atoms, heteroaryloxycarbonylalkylol groups with 3 to 20 carbon atoms, aminoalkylcarbonyl groups with 2 to 10 carbon atoms, arylyl groups with 7 to 20 carbon atoms, heteroarylyl groups with 1 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 10 carbon atoms, or aryloxycarbonyl groups with 7 to 20 carbon atoms.

[0213]

[0214] In equation (23), R 21a The term represents hydrogen, or optionally substituted alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 25 carbon atoms, heteroarylalkyl groups having 1 to 20 carbon atoms, alkoxycarbonylalkyl groups having 3 to 20 carbon atoms, phenoxycarbonylalkyl groups having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl groups having 1 to 20 carbon atoms or heteroarylthioalkyl groups, aminoalkyl groups having 1 to 20 carbon atoms, alkanolyl groups having 2 to 12 carbon atoms, enoyl groups having 3 to 25 carbon atoms, cycloalkanolyl groups having 3 to 8 carbon atoms, arylyl groups having 7 to 20 carbon atoms, heteroarylyl groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 20 carbon atoms, or cycloalkylalkyl groups having 1 to 10 carbon atoms.

[0215] R 21b It represents any substituent containing an aromatic ring or a heteroaromatic ring.

[0216] It should be noted that R 21a With R 21b They can form a ring together, and the linking groups can be alkylene groups with 1 to 10 carbon atoms, or polyvinyl groups (-(CH=CH), which can be selected by choice and have substituents). r -), Polyethynyl (-(C≡C)) r -) or groups formed by combining them (it should be noted that r is an integer from 0 to 3).

[0217] R 22a R represents the value of R in equation (22) above. 22 The same group.

[0218] R in the above general formula (22) 22 And R in the above general formula (23) 22a Preferred examples include alkylol groups with 2 to 12 carbon atoms, heteroarylalkylol groups with 1 to 20 carbon atoms, and cycloalkylol groups with 3 to 8 carbon atoms.

[0219] R in the above general formula (23) 21aPreferably, straight-chain alkyl or cycloalkyl groups such as unsubstituted methyl, ethyl, and propyl, or propyl groups substituted with N-acetyl-N-acetoxyamino groups are used.

[0220] In addition, R in the above general formula (23) 21b Preferred alternatives include optional substituted carbazoyl group, optional substituted thioxanthyl group, and optional substituted phenyl thioether group.

[0221] As a photopolymerization initiator for oxime ester compounds, R in the above general formula (23) is preferred for the aforementioned reasons. 21b The carbazoyl group is optionally substituted. Furthermore, a carbazoyl group having at least one group selected from the group consisting of an aryl group with 6 to 25 carbon atoms optionally substituted, an aryl carbonyl group with 7 to 25 carbon atoms optionally substituted, a heteroaryl group with 5 to 25 carbon atoms optionally substituted, a heteroaryl carbonyl group with 6 to 25 carbon atoms optionally substituted, and a nitro group is preferred. Particularly preferred is a carbazoyl group having at least one group selected from the group consisting of benzoyl, tolueneyl, naphthoyl, thiophene carbonyl, and a nitro group. Additionally, these groups are preferably bonded to the 3-position of the carbazoyl group.

[0222] Commercially available photopolymerization initiators for this type of oxime ester compound include: OXE-02 manufactured by BASF Corporation, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0223] As photopolymerization initiators of oxime ester compounds suitable for the present invention, the following examples of compounds can be cited, but are limited to these compounds.

[0224]

[0225]

[0226]

[0227] Examples of ketoxime ester compounds include compounds containing the structural moiety shown in the following general formula (24), and preferably ketoxime ester compounds shown in the following general formula (25).

[0228]

[0229] In the above general formula (24), R 24 R in the aforementioned general formula (22) 22 They have the same meaning.

[0230]

[0231] In the above general formula (25), R 23aThe terms represent substituted radicals, phenyl, alkyl with 1 to 20 carbon atoms, alkenyl with 2 to 25 carbon atoms, heteroarylalkyl with 1 to 20 carbon atoms, alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, alkylthioalkyl with 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl or heteroarylthioalkyl with 1 to 20 carbon atoms, aminoalkyl with 1 to 20 carbon atoms, alkolyl with 2 to 12 carbon atoms, enoyl with 3 to 25 carbon atoms, cycloalkanol with 3 to 8 carbon atoms, arylyl with 7 to 20 carbon atoms, heteroarylyl with 1 to 20 carbon atoms, alkoxycarbonyl with 2 to 10 carbon atoms, aryloxycarbonyl with 7 to 20 carbon atoms, or cycloalkylalkyl with 1 to 10 carbon atoms.

[0232] R 23b It represents any substituent containing an aromatic ring or a heteroaromatic ring.

[0233] It should be noted that R 23a Can be used with R 23b Together they form a ring, and the linking groups can be alkylene groups having 1 to 10 carbon atoms, or polyvinyl groups (-(CH=CH), which can be optionally substituted. r -), Polyethynyl (-(C≡C)) r -) or groups formed by combining them (it should be noted that r is an integer from 0 to 3).

[0234] R 24a The terms represent the substituted groups, which are alkylol groups with 2 to 12 carbon atoms, enoyl groups with 3 to 25 carbon atoms, cycloalkanol groups with 4 to 8 carbon atoms, benzoyl groups with 7 to 20 carbon atoms, heteroaryl groups with 3 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 20 carbon atoms, heteroaryl groups with 2 to 20 carbon atoms, or alkylaminocarbonyl groups with 2 to 20 carbon atoms.

[0235] R in the above general formula (24) 24 And R in the above general formula (25) 24a Preferred examples include alkylol groups with 2 to 12 carbon atoms, heteroarylalkylol groups with 1 to 20 carbon atoms, cycloalkanol groups with 3 to 8 carbon atoms, and arylyl groups with 7 to 20 carbon atoms.

[0236] R in the above general formula (25) 23a Preferably, unsubstituted ethyl, propyl, butyl, or ethyl or propyl substituted with methoxycarbonyl can be used.

[0237] In addition, R in the above general formula (25) 23b Preferably, carbazolyl or phenyl thioether groups can be substituted.

[0238] As ketoxime ester compounds suitable for use in the present invention, the following examples of compounds can be cited, but are limited to these compounds.

[0239]

[0240]

[0241] Commercially available photopolymerization initiators for this type of ketoxime ester compound include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0242] These oxime and ketoxime ester compounds are known compounds, for example, one of a series of compounds described in Japanese Patent Application Publication No. 2000-80068 and Japanese Patent Application Publication No. 2006-36750.

[0243] The above-mentioned photopolymerization initiators can be used alone or in combination with two or more.

[0244] 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; benzophenone derivatives such as benzophenone, michalcone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; and benzophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylacetophenone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)one, and 1-hydroxy-1- Acetophenone derivatives such as (p-dodecylphenyl)one, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)one; thioxanone derivatives such as thioxanone, 2-ethylthioxanone, 2-isopropylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 2,4-diethylthioxanone, and 2,4-diisopropylthioxanone; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzophenazine; and anthrone derivatives such as benzoanthrone.

[0245] Among these photopolymerization initiators, oxime ester derivatives are particularly preferred for the reasons mentioned above.

[0246] <Sensitizing pigment>

[0247] In photopolymerization initiators, sensitizing pigments that match the wavelength of the image exposure light source can be used, as needed, to improve sensing sensitivity. Examples of such sensitizing pigments include, for instance, the xanthane pigments described in Japanese Patent Application Publication Nos. 4-221958 and 4-219756; the heterocyclic coumarin pigments described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; the 3-ketocoumarin compounds described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; the pyrrole methylene pigments described in Japanese Patent Application Publication Nos. 6-19240; and Japanese Patent Application Publication Nos. 47-2528 and 54-155. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publication No. 292, Japanese Published Publication No. 45-37377, Japanese Published Publication No. 48-84183, Japanese Published Publication No. 52-112681, Japanese Published Publication No. 58-15503, Japanese Published Publication No. 60-88005, Japanese Published Publication No. 59-56403, Japanese Published Publication No. 2-69, Japanese Published Publication No. 57-168088, Japanese Published Publication No. 5-107761, Japanese Published Publication No. 5-210240, and Japanese Published Publication No. 4-288818.

[0248] Among these sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino group and a phenyl group within the same molecule are 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; benzophenone compounds such as 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)1,3,4-oxobenzoxazole are also preferred. Compounds containing p-dialkylaminophenyl, such as azoles, 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, (p-diethylaminophenyl)pyrimidine, etc., are particularly preferred, with 4,4'-dialkylaminobenzophenone being especially preferred.

[0249] Sensitizing pigments can be used alone or in combination with two or more.

[0250] (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, further preferably 4% by mass or more, generally 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency for improved sensitivity. In addition, by setting it to the aforementioned upper limit or below, there is a tendency for improved solubility of the unexposed portion in the developer.

[0251] The above upper and lower limits can be combined arbitrarily. For example, 1-30% by mass is preferred, 1-20% by mass is more preferred, 2-15% by mass is even more preferred, 3-10% by mass is still preferred, and 4-8% by mass is particularly preferred.

[0252] When using sensitized pigments, the proportion of the sensitized pigments in the photosensitive resin composition is typically 0 to 20% by mass, preferably 0 to 15% by mass, and more preferably 0 to 10% by mass of the total solid components of the photosensitive resin composition.

[0253] <(D) Pigment>

[0254] When the photosensitive resin composition of the present invention is used for the formation of pixels, black matrices, or colored spacers in a color filter, it preferably contains a (D) colorant. A colorant refers to the substance that colors the photosensitive resin composition of the present invention. Dyes and pigments can be used as colorants, but pigments are preferred from the perspectives of heat resistance and lightfastness.

[0255] As pigments, various colors such as blue, green, red, yellow, purple, orange, brown, and black pigments can be used. Furthermore, in terms of their structure, in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and pyrene pigments, various inorganic pigments can also be used.

[0256] Hereinafter, specific examples of pigments that can be used in this invention are indicated by pigment designations. It should be noted that terms such as "CI Pigment Red 2" listed below refer to the Dye Index (CI).

[0257] Examples of red pigments include CI pigments 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53: 3, 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 these, CI Pigment Red 48 is preferably 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferably CI Pigment Red 177, 209, 224, 254.

[0258] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI Pigment Blue 15:6 and 60 are more preferred.

[0259] Examples of green pigments include CI pigments 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 pigments 7, 36, and 58 are preferred.

[0260] Examples of yellow pigments include CI pigments 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, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, CI pigment yellows 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferred, and CI pigment yellows 83, 138, 139, 150, and 180 are more preferred.

[0261] Examples of orange pigments include CI pigments 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 pigments 38, 64, and 71 are preferred.

[0262] Examples of purple pigments include CI pigments 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 more preferred.

[0263] In the case of a photosensitive resin composition for a black matrix of color filters, a black pigment can be used as the (D) pigment. The black pigment can be formed alone or mixed with red, green, blue, or other pigments. Furthermore, these pigments can be suitably selected from inorganic or organic pigments and dyes.

[0264] Examples of pigments that can be mixed for the preparation of black pigments include Victoria Blue (42595), Auramine O (41000), and Catilon Brilliant Flavin (Basic). 13) Rhodamine 6GCP (45160), Rhodamine B (45170), Safranbolu OK70:100 (50240), Poppy Red X (42080), No.120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), SIGMAFAST Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), SIGMAFAST Red 4015 (12355), Lionol Red 7B4401 (15850), Fastogen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) (It should be noted that the numbers in parentheses above refer to the dye index (CI)).

[0265] Furthermore, for other pigments that can be mixed, if represented by CI numbers, examples include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61, 64; and 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.

[0266] 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, pyrene black, and lactam black.

[0267] When using black pigments in these (D) pigments, carbon black is preferred from the viewpoint of light-blocking rate and image characteristics. Examples of carbon black include the following.

[0268] Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, # 20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0269] Made by Degussa Co., Ltd.: Printex (registered trademark. The following are the same.) 3. Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, ColorBlack S170

[0270] Manufactured by Cabot Corporation: Monarch (registered trademark. The same applies hereinafter.) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630; REGAL (registered trademark. The same applies hereinafter.) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R; BLACK PEARLS 480, PEARLS 130; VULCAN (registered trademark) XC72R; ELFTEX (registered trademark) -8

[0271] Made by Birla: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAV EN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0272] As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments that mix red, green, and blue can be used as black pigments.

[0273] As pigments, barium sulfate, lead sulfate, titanium dioxide, yellow lead, iron oxide, and chromium oxide can also be used. These various pigments can also be used in combination. For example, to adjust chromaticity, green pigment can be used with yellow pigment, or blue pigment with purple pigment.

[0274] As for the average particle size of the pigment, when forming the color layer of the color filter, there is no particular limitation as long as the desired color rendering can be achieved. Depending on the type of pigment used, a range of 10 to 100 nm is preferred, and a range of 10 to 70 nm is more preferred. By making the average particle size of the pigment within the above range, there is a tendency to make the color characteristics of the liquid crystal display device manufactured using the photosensitive resin composition of the present invention of high quality.

[0275] The average particle size of the carbon black is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or more, for example, 20 to 50 nm, and more preferably 20 to 60 nm. By setting the average particle size below the aforementioned upper limit, scattering is reduced, and there is a tendency to suppress the reduction of color characteristics such as light-blocking properties and contrast. In addition, by setting the average particle size above the aforementioned lower limit, the amount of dispersant does not become excessive, and there is a tendency to improve dispersibility.

[0276] It should be noted that the average particle size of the aforementioned pigments containing carbon black can be determined 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 is taken as the particle size. Then, for more than 100 particles, the volume (mass) of each particle is approximated by a cuboid of the determined particle size, and the volume-average particle size is calculated and taken as the average particle size. It should be noted that the same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0277] When the photosensitive resin composition of the present invention contains a (D) colorant, it is preferable that it contains at least a pigment. Furthermore, dyes may also be used in combination, provided that this does not affect the effects of the present invention. Examples of dyes that may be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methyst dyes.

[0278] 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.

[0279] Examples of anthraquinone dyes include CI Bat 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.

[0280] In addition, examples of phthalocyanine dyes include CI Bat 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.

[0281] When the photosensitive resin composition of the present invention contains (D) pigment, the proportion of (D) pigment relative to the total solid components in the photosensitive resin composition is generally selected in the range of 1 to 70% by mass. Within this range, 20% by mass or more is more preferred, 30% by mass or more is even more preferred, 40% by mass or more is particularly preferred, and 60% by mass or less is even more preferred.

[0282] The above upper and lower limits can be combined arbitrarily. For example, 1-70% by mass is preferred, 20-70% by mass is more preferred, 30-60% by mass is even more preferred, and 40-60% by mass is particularly preferred.

[0283] The photosensitive resin composition of the present invention, as described below, can be used for various applications. In the case of forming a black matrix, it can be used as a (D) colorant, employing the aforementioned black colorants such as carbon black and titanium black, or it can be mixed with various colorants other than black to adjust it to black for use. Among these, carbon black is particularly preferred from the viewpoint of dispersion stability and light-blocking properties.

[0284] When the photosensitive resin composition of the present invention is used for black matrix formation, an increased concentration of black pigment is required to improve opacity. From this viewpoint, the content of black pigment relative to the total solid components 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.

[0285] The above upper and lower limits can be combined arbitrarily. For example, 40-70% by mass is preferred, 45-70% by mass is more preferred, and 50-65% by mass is even more preferred.

[0286] When the photosensitive resin composition of the present invention contains colorant (D), the proportion of colorant (D) relative to 100 parts by weight of alkali-soluble resin (A) is typically 20 parts by weight or more, preferably 30 parts by weight or more, more preferably 40 parts by weight or more, further preferably 60 parts by weight or more, even more preferably 80 parts by weight or more, particularly preferably 120 parts by weight or more, most preferably 160 parts by weight or more, and typically 500 parts by weight or less, preferably 300 parts by weight or less, more preferably 280 parts by weight or less. By setting the proportion of colorant (D) to the aforementioned lower limit or above, there is a tendency to easily suppress the decrease in solubility of the unexposed portion in the developer. In addition, by setting it to the aforementioned upper limit or below, there is a tendency to easily obtain the desired image film thickness.

[0287] The above upper and lower limits can be combined arbitrarily. For example, 20 to 500 parts by mass is preferred, 30 to 500 parts by mass is more preferred, 40 to 500 parts by mass is even more preferred, 60 to 300 parts by mass is even more preferred, 80 to 300 parts by mass is even more preferred, 120 to 280 parts by mass is particularly preferred, and 160 to 280 parts by mass is most preferred.

[0288] <Dispersant>

[0289] When the photosensitive resin composition of the present invention contains (D) pigment, the pigment is finely dispersed and its dispersion is stabilized. However, it is important to ensure the stability of quality, so it is preferable to also contain a dispersant.

[0290] As dispersants, polymeric dispersants with functional groups are preferred. Furthermore, from the perspective of dispersion stability, polymeric dispersants with functional groups such as carboxyl groups, phosphate groups, sulfonic acid groups, or their bases, primary, secondary, or tertiary amines, quaternary ammonium bases, and groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are preferred. Among these, polymeric dispersants with basic functional groups, such as primary, secondary, or tertiary amines, quaternary ammonium bases, and groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine, are particularly preferred. By using these polymeric dispersants with basic functional groups, there is a tendency to achieve good dispersibility.

[0291] Examples of polymeric dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed from monomers with amino groups and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, dehydrated sorbitol aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0292] Specific examples of such dispersants, by trade name, include EFKA (registered trademark, manufactured by EFKA Corporation), Disperbyk (registered trademark, manufactured by BYK Corporation), DISPARLON (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW or FLOWNON (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Inc.).

[0293] These polymeric dispersants can be used alone or in combination of two or more.

[0294] From the perspectives of adhesion and linearity, the dispersant preferably comprises a urethane-based polymeric dispersant and / or an acrylic-based polymeric dispersant having basic functional groups, and more preferably a urethane-based polymeric dispersant for adhesion. Furthermore, from the perspectives of dispersibility and shelf life, a polymeric dispersant having basic functional groups and polyester and / or polyether bonds is preferred.

[0295] The weight-average molecular weight (Mw) of the polymeric dispersant is typically 700 or more, preferably 1000 or more, and typically 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By setting it to the aforementioned upper limit value or less, there is a tendency for the alkaline developability to become good even at high pigment concentrations.

[0296] The above upper and lower limits can be combined arbitrarily. For example, 700 to 100,000 is preferred, 700 to 50,000 is more preferred, and 1,000 to 30,000 is even more preferred.

[0297] Examples of urethane and acrylic polymeric dispersants include the Disperbyk 160-167, 182 series (all urethane-based) and Disperbyk 2000, 2001 (all acrylic-based) (all manufactured by BYK Corporation). Particularly preferred examples of urethane-based polymeric dispersants having basic functional groups, polyester and / or polyether bonds, and a weight-average molecular weight of 30,000 or less include Disperbyk 167 and 182.

[0298] <Carbamate-based polymer dispersions>

[0299] If a specific example is a preferred chemical structure for a urethane-based polymeric dispersant, examples include: a dispersion 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 a tertiary amino group in the same molecule.

[0300] Examples of the aforementioned polyisocyanate compounds include aromatic diisocyanates such as terephthalic 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 methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate; 4,4'-methylenebis(cyclohexyl) isocyanate; and ω,ω'-diisocyanate. Alicyclic diisocyanates such as dimethylcyclohexane, xylene diisocyanate, aliphatic diisocyanates with aromatic rings such as α,α,α',α'-tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanate phenylmethane), tris(isocyanate phenyl)thiophosphate, and their trimers, aqueous adducts, and polyol adducts. Preferred examples of polyisocyanates are trimers of organic diisocyanates, and most preferred examples are trimers of toluene diisocyanate and trimers of isophorone diisocyanate. They can be used alone or in combination of two or more.

[0301] As a method for manufacturing isocyanate trimers, the following method can be used: For the aforementioned polyisocyanates, the isocyanate groups are partially trimerized using a suitable trimerizing catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. After the trimerization is stopped by adding a catalyst poison, the unreacted polyisocyanates are removed by solvent extraction and thin-film distillation to obtain the target polyisocyanate containing isocyanurate groups.

[0302] Examples of compounds having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000 include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and compounds formed by alkylalkoxylation of a single terminal hydroxyl group of these compounds with 1 to 25 carbon atoms, as well as mixtures of two or more of these compounds.

[0303] 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.

[0304] Examples of polyether diols include those obtained by reacting a mixture of ether-containing diols or other diols with dicarboxylic acids or their anhydrides, or by reacting polyester diols with epoxides, such as poly(polyoxytetramethylene) adipate. The most preferred examples of polyether diols are those obtained by reacting polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds obtained by alkoxylating a single terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.

[0305] 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 mixed 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, 2-ethyl-2-prop ... Polyols obtained by polycondensation of aliphatic diols such as methyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylenediol, 2-methyl-1,8-octamethylenediol, and 1,9-nonanediol; alicyclic diols such as dihydroxymethylcyclohexane; xylene glycol; aromatic diols such as dihydroxyethoxybenzene; and N-alkyldialkylolamines such as N-methyldiethanolamine; such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate; or polylactone diols or polylactone monools obtained by using the aforementioned diols or monohydric alcohols with 1 to 25 carbon atoms as initiators, such as polycaprolactone diol, polymethylvalerol, and mixtures of two or more thereof. The most preferred example of a polyester diol is polycaprolactone diol or polycaprolactone using an alcohol with 1 to 25 carbon atoms as an initiator.

[0306] Examples of polycarbonate diols include poly(1,6-hexene)carbonate and poly(3-methyl-1,5-pentene)carbonate; examples of polyolefin diols include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.

[0307] They can be used individually or in combination with two or more.

[0308] The number 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 more preferably 1,000 to 4,000.

[0309] Next, compounds having active hydrogen and tertiary amino groups within the same molecule will be described. Examples of active hydrogen, i.e., hydrogen atoms directly bonded to oxygen, nitrogen, or sulfur atoms, include hydrogen atoms in functional groups such as hydroxyl, amino, and mercapto groups, with hydrogen atoms in amino groups being preferred, and hydrogen atoms in primary amino groups being particularly preferred.

[0310] Tertiary amines are not particularly limited; examples include amines with alkyl groups having 1 to 4 carbon atoms, or heterocyclic structures, more specifically imidazole rings or triazole rings.

[0311] Examples of compounds having both active hydrogen and tertiary amino 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.

[0312] Examples of nitrogen-containing heterocycles when the tertiary amine is a nitrogen-containing heterocycle include pyrazole rings, imidazole rings, triazole rings, tetraazole rings, indole rings, carbazole rings, indazole rings, benzimidazole rings, benzotriazole rings, benzoxazole rings, benzothiazole rings, benzothiadiazole rings, and other nitrogen-containing five-membered heterocycles, as well as pyridine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings, isoquinoline rings, and other nitrogen-containing six-membered heterocycles. Among these nitrogen-containing heterocycles, imidazole rings or triazole rings are preferred.

[0313] Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazolium, histidine, 2-aminoimidazolium, and 1-(2-aminoethyl)imidazolium. Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. 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.

[0314] They can be used individually or in combination with two or more.

[0315] The preferred mixing ratio of raw materials for manufacturing carbamate-based polymeric dispersants is as follows relative to 100 parts by mass of a polyisocyanate compound: 10-200 parts by mass of a compound having one or two hydroxyl groups within the same molecule and a number average molecular weight of 300-10000, preferably 20-190 parts by mass, more preferably 30-180 parts by mass; and 0.2-25 parts by mass of a compound having active hydrogen and tertiary amino groups within the same molecule, preferably 0.3-24 parts by mass.

[0316] The manufacture of urethane-based polymeric dispersants can be carried out according to known methods for the manufacture of polyurethane resins. Solvents used in the manufacture 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, sec-butanol, and tert-butanol; 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 can be used individually or in combination.

[0317] In the above-mentioned 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 acetylacetone and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0318] <Methods for determining amine value>

[0319] The tertiary amine value of a dispersant is expressed as the mass of KOH equal to the amount of alkali per 1g of solid component of the sample after removing the solvent from the dispersant. It can be determined by the following method.

[0320] 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, titrate the solution with a 0.1 mol / L HClO4 (perchloric acid) acetic acid solution. Take the inflection point of the pH titration curve as the titration endpoint and calculate the amine value according to the following formula.

[0321] Amine value [mgKOH / g] = (561 × V) / (W × S)

[0322] [Where, W: represents the weight of the dispersant sample [g], V: represents the titration volume at the titration endpoint [mL], and S: represents the concentration of the solid component of the dispersant sample [mass %].]

[0323] The amount of compounds containing both active hydrogen and tertiary amino groups within the same molecule is preferably controlled within the range of 1 to 100 mg KOH / g, based on the amine value after the reaction. More preferably, it is within the range of 5 to 95 mg KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by titrating a basic amino group with an acid for neutralization. By setting the amine value above the aforementioned lower limit, there is a tendency for improved dispersibility. Conversely, by setting it below the aforementioned upper limit, there is a tendency for improved developability.

[0324] In the above reaction, if isocyanate groups remain in the polymeric dispersant, and the isocyanate groups are then consumed by alcohols or amino compounds, the product's stability over time becomes higher, which is therefore preferred.

[0325] The weight-average molecular weight (Mw) of urethane-based polymeric dispersants is typically in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. It is particularly preferred to be below 30,000. By setting it to the aforementioned lower limit or above, there is a tendency for improved dispersibility and dispersion stability. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency for improved solubility. The aforementioned upper and lower limits can be combined arbitrarily. 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 good alkaline developability, especially at high pigment concentrations. Examples of such particularly preferred commercially available urethane dispersants include Disperbyk 167 and 182 (BYK Corporation).

[0326] When the photosensitive resin composition of the present invention contains a dispersant, the proportion of the dispersant in the total solid components of the photosensitive resin composition is typically 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, typically 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 particularly 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, even more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.

[0327] Furthermore, the proportion of the dispersant relative to 100 parts by weight of the (D) colorant is typically 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and 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, 5 to 200 parts by weight is preferred, 10 to 80 parts by weight is more preferred, and 15 to 50 parts by weight is even more preferred.

[0328] By setting the value above the aforementioned lower limit, there is a tendency to easily ensure sufficient dispersion. Conversely, by setting the value below the aforementioned upper limit, there is a tendency to easily achieve sufficient color concentration, sensitivity, and film-forming properties without reducing the proportion of other components.

[0329] <Thiols>

[0330] The photosensitive resin composition of this invention preferably contains sulfur-containing alcohols to enhance sensitivity and improve adhesion to the substrate. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene glycol dimercaptopropionate, butylene glycol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butylene glycol bis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane; (trade name: Karenz MT) BD1 (manufactured by Showa Denko Co., Ltd.), butylene glycol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate); (trade name: Karenz MT PE1, manufactured by Showa Denko Co., Ltd.), 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-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.). Each of these can be used alone or in combination of two or more.

[0331] Preferred polyfunctional thiols include PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1, with Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 being the most preferred, and Karenz MT PE1 being the most particularly preferred.

[0332] When using a thiol compound, the proportion of the thiol compound 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 aforementioned lower limit or above, there is a tendency to suppress the decrease in sensitivity. In addition, by setting it to the aforementioned upper limit or below, there is a tendency to easily maintain good storage stability.

[0333] The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferred, 0.3 to 10% by mass is more preferred, and 0.5 to 5% by mass is even more preferred.

[0334] <Solvent>

[0335] The photosensitive resin composition of the present invention is generally used in a state in which various materials comprising (A) alkali-soluble resin, (B) photopolymerizable monomer and (C) photopolymerization initiator, and (D) colorant as needed are dissolved or dispersed in an organic solvent.

[0336] As a solvent, sometimes the organic solvent used in the manufacturing method of the present invention, or the organic solvent contained in the liquid containing carboxyl-containing resin of the present invention, is used directly.

[0337] As an organic solvent, it is preferable to select one with a boiling point (under a pressure of 1013.25 hPa. Hereinafter, the same applies to boiling point.) in the range of 100 to 300°C. Solvents with a boiling point of 120 to 280°C are more preferred.

[0338] Examples of such organic solvents include the following.

[0339] 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 tert-butyl 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 diethylene glycol monoalkyl ethers;

[0340] Diethylene glycol dialkyl ethers, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0341] 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, 3-methyl-3-methoxybutyl acetate, and other diol alkyl ether acetates;

[0342] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate;

[0343] Alkyl acetates such as cyclohexanol acetate;

[0344] Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0345] Ketones such as acetone, methyl ethyl ketone, methyl pentanone, methyl isopropanone, methyl isopentanone, diisopropanone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentanone, methyl butyl ketone, methyl hexanone, methyl nonanone, and methoxymethyl pentanone;

[0346] 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;

[0347] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0348] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl;

[0349] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0350] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, 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;

[0351] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0352] Halogenated hydrocarbons such as butyl chloride and pentyl chloride;

[0353] Ether ketones such as methoxymethylpentanone;

[0354] Nitriles such as acetonitrile and benzonitrile;

[0355] Examples of commercially available solvents falling under the aforementioned categories include mineral oils, Varsol #2, Apco #18 solvent, Apco thinner, Sokal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark. The same applies hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and Diglyme (all trade names).

[0356] These organic solvents can be used alone or in combination of two or more.

[0357] When forming the pixels or black matrix of a color filter using photolithography, the organic solvent preferably has a boiling point in the range of 100–250°C. More preferably, it has a boiling point in the range of 120–230°C.

[0358] Among the aforementioned organic solvents, diol alkyl ether acetates are preferred due to their good coatability, surface tension balance, and high solubility of the constituent components in the composition.

[0359] Diol alkyl ether acetates can be used alone or in combination with other organic solvents. Among these, monoalkyl glycol ethers are particularly preferred, considering the solubility of the components in the composition. Monoalkyl glycol ethers tend to have high polarity, and if added in excessive amounts, the pigments tend to aggregate, leading to a gradual increase in the viscosity of the resulting photosensitive resin composition and decreased storage stability. Therefore, the proportion of monoalkyl glycol ethers in the solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0360] 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 photosensitive resin composition becomes less prone to drying, but it also prevents the uniform dispersion of the pigments in the composition from being destroyed due to rapid drying. That is, for example, it has the effect of preventing foreign matter defects caused by the precipitation / curing of pigments at the tip of the slit nozzle. From the perspective of high effectiveness, 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, triacetylglycerol, and 1,6-hexanediol diacetate are particularly preferred.

[0361] The content of the high-boiling-point solvent in the organic solvent is preferably 0% to 50% by mass, more preferably 0.5% to 40% by mass, and particularly preferably 1% to 30% by mass. By setting it to the aforementioned lower limit or above, there is a tendency to suppress, for example, the occurrence of foreign matter defects caused by precipitation / curing of pigments at the tip of the slit nozzle. In addition, by setting it to the aforementioned upper limit or below, there is a tendency to suppress problems such as slow drying temperature of the composition, poor production contact in the color filter manufacturing process, and pin marks in the pre-baked process.

[0362] In the photosensitive resin composition of the present invention, the proportion of organic solvent is not particularly limited. From the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. In addition, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0363] <Other Components in the Formulation of the Photosensitive Resin Composition>

[0364] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may also be appropriately mixed with adhesion improvers, coatability improvers, pigment derivatives, developer improvers, ultraviolet absorbers, antioxidants, etc.

[0365] <Sealing Improver>

[0366] To improve adhesion to the substrate, an adhesion improver may be included, such as silane coupling agents and titanium coupling agents, with silane coupling agents being particularly preferred.

[0367] 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 Silicone Co., Ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dowing Corp.). It should be noted that a single silane coupling agent can be used, or two or more can be used in any combination and ratio.

[0368] Furthermore, the photosensitive resin composition of the present invention may also contain a binding improver other than a silane coupling agent, such as a phosphoric acid binding improver or other binding improvers.

[0369] As a phosphate-based binding improver, phosphate esters containing (meth)acryloyloxy groups are preferred, among which those shown in the following general formulas (g1), (g2), and (g3) are preferred.

[0370]

[0371] In the above general formulas (g1), (g2), and (g3), R 51 Each of them 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.

[0372] Other seal improvers include TEGO*Add Bond LTH (manufactured by Evonik). These phosphate-containing compounds and other seal improvers can be used alone or in combination of two or more.

[0373] When the photosensitive resin composition of the present invention contains an adhesion improver, the proportion of the adhesion improver 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 of the total solid components in the photosensitive resin composition. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve adhesion. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to improve developability.

[0374] The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferred, 0.01 to 3% by mass is more preferred, 0.1 to 2% by mass is even more preferred, and 0.5 to 1.5% by mass is particularly preferred.

[0375] <Coating performance improver>

[0376] In the photosensitive resin composition of the present invention, a surfactant may be included as a coating improver to improve coatability. Examples of surfactants include anionic, cationic, nonionic, and amphoteric surfactants. Nonionic surfactants are preferred where the likelihood of adverse effects on various properties is low, and fluorinated or silicone surfactants are effective in improving coatability.

[0377] Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS COMPANY LIMITED), BYK-300, BYK-325, BYK-330 (manufactured by BYK Corporation), KP340 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Toray Dowing Corp.), DS-401 (manufactured by DAIKIN INDUSTRIES, LTD.), L-77 (manufactured by Nippon Unicar Company Limited), and FC4430 (manufactured by 3M Japan Corporation). It should be noted that a single surfactant can be used, or two or more surfactants can be used in any combination and ratio.

[0378] When the photosensitive resin composition of the present invention contains a surfactant, the proportion of the surfactant in the photosensitive resin composition is not particularly limited. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1.0% by mass or less, more preferably 0.7% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency for the resin coating uniformity to become better. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency for the resin sensitivity not to decrease.

[0379] The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferred, 0.01 to 0.7% by mass is more preferred, 0.05 to 0.5% by mass is even more preferred, and 0.05 to 0.3% by mass is particularly preferred.

[0380] <Pigment Derivatives>

[0381] In order 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, dioxazine, anthraquinone, indanthrene, pyrene, violetone, diketopyrrolopyrrole, and dioxazine derivatives, among which phthalocyanine and quinophthalone derivatives are preferred.

[0382] Examples of substituents for pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are directly bonded to the pigment skeleton or 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 diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. They can be used individually or in combination of two or more.

[0383] 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 more preferably 5% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve dispersion stability. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to improve developability.

[0384] The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferred, 0.5 to 10% by mass is more preferred, and 1.0 to 5% by mass is even more preferred.

[0385] <Physical Properties of Photosensitive Resin Compositions>

[0386] The photosensitive resin composition of the present invention is suitable for use in forming a black matrix, and from the above viewpoint, it is preferably black. Furthermore, the optical density (OD) per 1 μm film thickness is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.5 or more, even more preferably 3.0 or more, particularly preferably 4.0 or more, and most preferably 4.5 or more, typically 6.0 or less, for example, preferably 1.0 to 6.0, more preferably 2.0 to 6.0, further preferably 2.5 to 6.0, even more preferably 3.0 to 6.0, particularly preferably 4.0 to 6.0, and most preferably 4.5 to 6.0. By setting it to the aforementioned lower limit value or above, there is a tendency to ensure sufficient light-blocking properties.

[0387] <Method for manufacturing photosensitive resin composition>

[0388] When the photosensitive resin composition of the present invention contains a (D) pigment, the (D) pigment is preferably pre-dispersed using a paint container, sand mill, ball mill, roller mill, crusher, spray mill, homogenizer, or the like. Through dispersion treatment, the (D) pigment is micronized, thus improving the coating properties of the resin. Furthermore, using a black pigment as the (D) pigment is beneficial for improving light-blocking ability.

[0389] The dispersion treatment is preferably carried out in a system comprising (D) pigment, organic solvent and dispersant as needed, and part or all of (A) alkali-soluble resin. (Hereinafter, the mixture supplied for the dispersion treatment and the composition obtained in the dispersion treatment are sometimes referred to as "ink" or "pigment dispersion".) If a polymeric dispersant is used as the dispersant, the thickening of the resulting ink and resin over time is suppressed (excellent dispersion stability), which is therefore particularly preferred.

[0390] When dispersing a body fluid containing all the components blended in a photosensitive resin composition, there is a possibility that highly reactive components may be modified due to the exothermic reaction generated during the dispersion process. Therefore, it is preferable to perform the dispersion process using a system containing a polymeric dispersant.

[0391] When dispersing (D) pigment using a sand mill, glass beads or zirconia beads with a diameter of approximately 0.1 to 8 mm are preferred. Dispersion conditions are as follows: temperature is typically 0°C to 100°C, preferably room temperature to 80°C. The optimal dispersion time varies depending on the composition of the liquid and the size of the dispersion apparatus, and therefore should be adjusted accordingly. The goal of dispersion is to control the ink's gloss within a range of 100 to 200, based on the resin's 20-degree specular gloss (JIS Z8741). If the resin's gloss is low, the dispersion is insufficient, resulting in a large amount of coarse pigment particles remaining, potentially leading to insufficient developability, adhesion, and resolution. Furthermore, if dispersion is continued until the gloss value exceeds the aforementioned range, the pigment breaks down, producing a large number of ultrafine particles, thus potentially impairing dispersion stability.

[0392] Next, the components contained in the photosensitive resin composition, namely (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) pigment, are mixed with the ink obtained through the above dispersion treatment and stirred at a temperature of 20–30°C to form a homogeneous solution. In the manufacturing process of the photosensitive resin composition, most fine dust particles are mixed in the liquid; therefore, it is desirable to filter the obtained resin using a filter or the like.

[0393] [ink]

[0394] The method for manufacturing the ink of the present invention comprises (A) an alkali-soluble resin, an organic solvent, and (D) a pigment. The method includes the following steps: mixing a carboxyl-containing resin manufactured by the method of the present invention as (A) the alkali-soluble resin. A dispersant may be added to the ink as needed.

[0395] Organic solvents, (D) pigments, and dispersants may be preferred for use in the photosensitive resin composition.

[0396] <Ink Manufacturing Method>

[0397] The ink in this invention is obtained, for example, by the dispersion treatment described in the method for manufacturing a photosensitive resin composition.

[0398] [cured material]

[0399] The method for manufacturing the cured product of the present invention includes the following steps: curing the photosensitive resin composition obtained in the manufacturing method of the present invention.

[0400] The cured product obtained by curing a photosensitive resin composition can be used as a component for color filters such as pixels, black matrices, and color spacers.

[0401] [Black Matrix]

[0402] The method for manufacturing the black matrix of the present invention includes the following steps: forming a black matrix using the cured material obtained in the manufacturing method of the present invention.

[0403] The black matrix of the cured material obtained using the manufacturing method of the present invention will be described according to the manufacturing method thereon.

[0404] (1) Support

[0405] As a support for forming the black matrix, the material is not particularly limited as long as it has adequate strength. A transparent substrate is primarily used, and materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic acid resins, and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. Furthermore, transparent electrodes such as ITO and IZO can be formed on the surface of the substrate. Electrodes can also be formed outside the transparent substrate, for example, on a TFT array.

[0406] For the support, in order to improve surface properties such as adhesion, various resin film formation treatments such as corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, and urethane resin can be performed as needed.

[0407] The thickness of the transparent substrate is typically 0.05 to 10 mm, preferably 0.1 to 7 mm. Furthermore, when performing thin film formation processes with various resins, the film thickness is typically 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0408] (2) Black Matrix

[0409] As a method for forming a black matrix from a cured product obtained by the manufacturing method of the present invention, one example is a method for forming a black matrix from a cured product obtained by curing a photosensitive resin composition obtained by the manufacturing method of the present invention. For example, a method is as follows: after coating a transparent substrate with the photosensitive resin composition of the present invention and drying it, a photomask is placed on the dried sample, and image exposure, development, and thermal or photocuring are performed through the photomask to form a black matrix.

[0410] (3) Formation of the black matrix

[0411] (3-1) Coating of the photosensitive resin composition

[0412] The photosensitive resin composition for black matrix can be coated onto a transparent substrate using methods such as spin coating, wire-wound bar coating, flow coating, die coating, roll coating, or spray coating. Among these methods, die coating is preferred from the overall viewpoint of significantly reducing the amount of coating liquid used, eliminating the effects of adhering mist as in spin coating, and suppressing the generation of foreign matter.

[0413] The thickness of the coating, measured by the dried film thickness, 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. By setting it below the aforementioned upper limit, pattern development becomes easier, and gap adjustment in the liquid crystal unitization process also becomes easier. By setting it above the aforementioned lower limit, desired color performance tends to become easier.

[0414] (3-2) Drying of the coating

[0415] Drying the coating film after applying the photosensitive resin composition to the substrate is preferably based on a drying method using a hot plate, IR oven, or 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 is typically selected within the range of 15 seconds to 5 minutes at a temperature of 40–200°C, preferably within the range of 30 seconds to 3 minutes at a temperature of 50–130°C, depending on the type of solvent components and the performance of the dryer used.

[0416] 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 will decompose, inducing thermal polymerization and sometimes resulting in poor development. It should be noted that the drying process of this coating can be a vacuum drying method, which involves drying in a vacuum chamber without raising the temperature.

[0417] (3-3) Exposure

[0418] Image exposure is performed as follows: a negative mask pattern is superimposed on a coating of the photosensitive resin composition, and light of wavelengths from the ultraviolet to the visible region is irradiated through the mask pattern. At this time, if necessary, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer can be formed on the photopolymerizable coating before exposure. The light source used in the above image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. When irradiating light of a specific wavelength, an optical filter can also be used.

[0419] (3-4) Development

[0420] The black matrix in this invention can be fabricated as follows: after exposing a coating obtained from a photosensitive resin composition to an image using the aforementioned light source, an image is formed on a substrate by developing an aqueous solution containing an organic solvent, or a surfactant and an alkaline compound. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0421] Examples of basic compounds include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic basic compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono-, or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds can be used alone or in mixtures of two or more.

[0422] 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.

[0423] 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.

[0424] There are no particular restrictions on the conditions for development. The development temperature is usually in the range of 10 to 50°C, with 15 to 45°C being particularly preferred, and 20 to 40°C being especially preferred. The development method can be any method based on immersion development, spray development, brush development, ultrasonic development, etc.

[0425] (3-5) Thermosetting treatment

[0426] After development, the substrate is subjected to thermal curing or photocuring, preferably thermal curing. The thermal curing conditions are as follows: temperature in the range of 100 to 280°C, preferably in the range of 150 to 250°C, and time in the range of 5 to 60 minutes.

[0427] The height of the black matrix formed above is typically 0.5–5 μm, preferably 0.8–4 μm.

[0428] Furthermore, the optical density (OD) per 1 μm thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.

[0429] [Formation of other color filters]

[0430] On a transparent substrate with a black matrix, a photosensitive resin composition containing one of the colors red, green, and blue is coated using the same process as described in steps (3-1) to (3-5) above. After drying, a photomask is superimposed on the coating. Through the photomask, an image is exposed, developed, and then thermally or photocured as needed to form a pixel image, thus creating a color layer. This process is performed on the red, green, and blue photosensitive resin compositions separately to form a color filter. The order in which they are applied is not limited to those described above.

[0431] [Colored spacers]

[0432] The photosensitive resin composition obtained in the manufacturing method of the present invention can be used as a resin for coloring spacers, in addition to the black matrix. When spacers are used in TFT-type LCDs, since light incident on the TFT sometimes causes malfunctions as a switching element, the coloring spacers are used to prevent this. For example, Japanese Patent Application Publication No. 8-234212 discloses that the spacers are light-shielding. Besides using a mask for coloring spacers, the coloring spacers can also be formed using the same method as the aforementioned black matrix.

[0433] (3-6) Formation of transparent electrodes

[0434] In its original state, color filters form transparent electrodes such as ITO on the image and are used as part of components such as color displays and liquid crystal display devices. However, to improve surface smoothness and 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 orientation driving methods (IPS mode), transparent electrodes are sometimes not formed.

[0435] [Separator]

[0436] The photosensitive resin composition obtained in the manufacturing method of the present invention, or the photosensitive resin composition of the present invention, can also be used to form a partition wall, particularly a partition wall for dividing the organic layer of an organic electroluminescent element. Examples of organic layers used in organic electroluminescent elements include those described in Japanese Patent Application Publication No. 2016-165396, which are used in hole injection layers, hole transport layers, or hole transport layers on hole injection layers.

[0437] The partition wall using the photosensitive resin composition obtained by the manufacturing method of the present invention or the photosensitive resin composition of the present invention will be described according to its manufacturing method.

[0438] (4-1) Support

[0439] As the support and substrate for forming the partition wall, the same support and substrate as those described above for forming the black matrix can be used.

[0440] (4-2) partition wall

[0441] Hereinafter, specific examples of methods for forming a partition wall using a photosensitive resin composition obtained in the manufacturing method of the present invention or a photosensitive resin composition of the present invention will be described for use as a partition wall.

[0442] Typically, a photosensitive resin composition is applied to a substrate where partitions are to be formed using methods such as coating to form a film or pattern, followed by solvent drying. Then, the pattern is formed using methods such as photolithography, which involves exposure and development.

[0443] Subsequently, additional exposure and thermal curing processes are performed as needed to form partition walls on the substrate.

[0444] (4-3) Formation of the partition wall

[0445] The specific methods of supplying the photosensitive resin composition to the substrate, drying, exposure, development, additional exposure, and thermal curing in the method of forming the partition wall of the photosensitive resin composition obtained by the manufacturing method of the present invention can be the same as those for forming the black matrix described above.

[0446] When used as a separator, its size and shape can be adjusted appropriately according to the method of applying it to organic light-emitting elements, but the height of the separator formed by the photosensitive resin composition is usually about 0.5 to 10 μm.

[0447] [Corrective LED]

[0448] The organic electroluminescent element of the present invention comprises a cured material obtained by the manufacturing method of the present invention, such as a partition wall.

[0449] For example, various organic light-emitting elements can be manufactured using a substrate having a partition wall pattern manufactured by the above method. The method for forming the organic light-emitting element is not particularly limited, but preferably involves forming an organic layer such as a pixel using a wet process such as vapor deposition, casting, spin coating, or inkjet printing, after forming a partition wall pattern on the substrate by the above method, whereby a functional material is sublimated in a vacuum state, adhered to the area enclosed by the partition walls on the substrate, and formed into a film.

[0450] Types of organic light-emitting elements include bottom-emitting and top-emitting types.

[0451] In bottom-emitting types, for example, a partition wall is formed on a glass substrate with stacked transparent electrodes, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition wall. On the other hand, in top-emitting types, for example, a partition wall is formed on a glass substrate with stacked metal electrode layers, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the partition wall.

[0452] Examples of organic electroluminescent layers include those described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681. Alternatively, quantum dots described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101 can also be used.

[0453] The layer composition is not limited to this. For example, from the viewpoint of luminous efficiency, each layer of the hole transport layer and electron transport layer can be a stack of two or more layers. The thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is usually 1 to 500 nm.

[0454] Organic electroluminescent elements can be formed with each opening displaying RGB colors, or with two or more colors stacked in a single opening. From a reliability perspective, organic electroluminescent elements can incorporate a sealing layer. This sealing layer prevents moisture from the air from adsorbing onto the organic electroluminescent element and reducing its luminous efficiency. From a light extraction efficiency perspective, organic electroluminescent elements can also incorporate a low-reflection film at the air interface. By placing the low-reflection film at the air-element interface, it is expected to reduce the refractive index gap or suppress reflection at the interface. For example, moth-eye structures and multilayer film techniques can be used for such low-reflection films.

[0455] When using organic light-emitting elements as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of one pixel from leaking into other pixels. Furthermore, it is necessary to prevent the image quality from being reduced due to the reflection of external light when the electrodes or the like are made of metal. Therefore, it is preferable to give the partition wall constituting the organic light-emitting element light-shielding properties.

[0456] In organic electroluminescent elements, electrodes need to be applied to the upper and lower surfaces of the separator. Therefore, from the viewpoint of insulation, the separator is preferably high in resistance and low in dielectric constant. Thus, when using a colorant to impart light-shielding properties to the separator, the aforementioned organic pigment, which has high resistance and low dielectric constant, is preferably used.

[0457] [Image display device]

[0458] The manufacturing method of the image display device of the present invention is characterized by using the cured material obtained in the manufacturing method of the present invention, or the black matrix obtained in the manufacturing method of the present invention.

[0459] Furthermore, the image display device of the present invention includes a cured product 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 cured product obtained by curing the photosensitive resin composition of the present invention. As a manufacturing method thereof, examples include manufacturing methods of cured products, black matrices, and partition walls formed using the photosensitive resin composition obtained by the manufacturing method of the present invention or formed from the photosensitive resin composition of the present invention.

[0460] As an image display device in this invention, it is not particularly limited to any device that displays images or videos, and examples include liquid crystal display devices and organic EL displays described later.

[0461] Liquid crystal display device

[0462] The liquid crystal display device of the present invention has the black matrix of the present invention, and the formation order and formation position of the color pixels and the black matrix are not particularly limited.

[0463] Liquid crystal display devices are typically manufactured as follows: an alignment film is formed on a color filter; spacers are dispersed on the alignment film; it is then bonded to an opposing substrate to form a liquid crystal cell; liquid crystal is injected into the formed liquid crystal cell; and the cell is then connected to an opposing electrode. Resin films such as polyimide are suitable as alignment films. Gravure printing and / or flexographic printing are commonly used to form the alignment film, with a thickness of several tens of nanometers. After curing the alignment film through thermal firing, surface treatment is performed by ultraviolet irradiation and the application of a friction cloth to achieve a surface condition that allows for adjustment of the liquid crystal slope.

[0464] As spacers, spacers with a size matching the gap between the substrate and the opposing substrate are typically suitable, usually ranging from 2 to 8 μm. Photolithographic spacers (PS), formed by photolithography on a color filter substrate using a transparent resin film, can also be used instead of spacers. As the opposing substrate, array substrates are commonly used, with TFT (thin-film transistor) substrates being particularly suitable.

[0465] The gap between the liquid crystal display (LCD) cell and the opposing substrate varies depending on the application of the LCD device, but is typically selected within the range of 2–8 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 cured by UV irradiation and / or heating, thus sealing the periphery of the liquid crystal cell.

[0466] After the liquid crystal cell with its perimeter sealed is cut into panel units, a pressure reduction is created within the vacuum chamber. This causes the liquid crystal injection port to be immersed in liquid crystal, and leakage occurs within the chamber, thereby injecting the liquid crystal into the liquid crystal cell. The pressure reduction within the liquid crystal cell is typically 1 × 10⁻⁶. -2 ~1×10 -7 Pa, but preferably 1×10 -3 ~1×10 -6 Pa. Furthermore, it is preferable to heat the liquid crystal cell under reduced pressure, with the heating temperature typically ranging from 30 to 100°C, more preferably from 50 to 90°C. The heating under reduced pressure is typically maintained for 10 to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell, now filled with liquid crystal, is cured with UV-curable resin, and the liquid crystal injection port is sealed, thus completing the liquid crystal display device (panel).

[0467] There are no particular restrictions on the type of liquid crystal; it can be any known liquid crystal such as aromatic, aliphatic, or polycyclic compounds, as well as lyotropic and thermotropic liquid crystals. Among thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known and can all be used.

[0468] [Organic EL Display]

[0469] The organic EL display of the present invention is manufactured using the color filter and organic electroluminescent element of the present invention.

[0470] When using the color filter of the present invention to fabricate an organic EL display, for example, as shown in the figure... Figure 1 As shown, firstly, a color filter is formed on a transparent support substrate 10 by forming a pattern (i.e., pixels 20 and a resin black matrix (not shown)) of a photosensitive resin composition. An organic light-emitting element 500 is then stacked on this color filter with an organic protective layer 30 and an inorganic oxide film 40 in between, thereby fabricating an organic EL element 100. It should be noted that at least one of the pixels 20 and the resin black matrix is ​​made using the photosensitive resin composition of the present invention. Examples of methods for stacking the organic light-emitting element 500 include: sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter; attaching the formed organic light-emitting element 500 to an inorganic oxide film 40 on another substrate; and so on. Using the organic EL element 100 manufactured in this way, an organic EL display can be manufactured, for example, by the method described in "Organic EL Display" (Ohmsha, Ltd., published on August 20, 2004, written by Shizushi Tokito, Chinatsuya Adachi, and Hideyuki Murata).

[0471] It should be noted that the color filter in this invention can be used in passive-drive organic EL displays or active-drive organic EL displays.

[0472] [Methods for controlling the molecular weight of carboxyl-containing resins]

[0473] The method for controlling the molecular weight of the carboxyl-containing resin of the present invention includes the following steps: controlling the water content of a first liquid containing reaction product A obtained by reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent to obtain a second liquid containing reaction product A; adding a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) to the aforementioned second liquid containing reaction product A and reacting them to obtain a carboxyl-containing resin.

[0474] In detail, it is the same as step B and step C in the method for manufacturing carboxyl-containing resin of the present invention.

[0475] To obtain a carboxyl-containing resin, a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) can be added to a second liquid containing reaction product A and reacted to obtain the resin.

[0476] The preferred types and preferred blending 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 in the method for manufacturing carboxyl-containing resins.

[0477] The organic solvent used in the reaction to obtain the first liquid containing reaction product A is preferably the organic solvent used in the method for manufacturing the carboxyl-containing resin of the present invention.

[0478] Example

[0479] The present invention is illustrated by examples, but the invention is not limited to the following examples as long as it does not deviate from its spirit.

[0480] <Examples 1-4: Synthesis of carboxyl-containing resins (1)-(4)>

[0481]

[0482] In a flask equipped with a thermometer, stirrer, and condenser, 265 g of the epoxy compound with the above-described 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 placed. The mixture was stirred and reacted at 100°C until the acid value became below 5 mg KOH / g. The reaction took 9 hours, yielding a liquid containing the intermediate and the first reaction product A.

[0483] After cooling the first liquid containing reaction product A to 50°C, the water content was measured using a Karl Fischer moisture meter (Kyoto Electronics Industry Co., Ltd., MKA-610). Water was added to the first liquid containing reaction product A at 50°C while stirring to control the water content of the liquid containing reaction product A, so as to achieve the water content rate recorded in Table 1.

[0484] In the above-mentioned liquid containing the second reaction product A with controlled moisture content, 10g of trimethylolpropane (TMP), 112g of biphenyltetracarboxylic acid dianhydride (BPDA), 105g of tetrahydrophthalic anhydride (THPA), and 374g of PGMEA were placed in 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 liquids containing carboxyl-containing resins (1) to (4).

[0485] The weight-average molecular weights (Mw) of the carboxyl-containing resins (1) to (4) obtained by GPC (Waters Corporation, 2695) and converted from polystyrene are recorded in Table 1.

[0486] [Table 1]

[0487]

[0488] As can be seen from Examples 1 to 4 shown in Table 1, by having a process for controlling the moisture content of the liquid containing reaction product A, the weight-average molecular weight of the carboxyl-containing resin can be controlled.

[0489] Thus, according to the manufacturing method of the present invention, the molecular weight of the carboxyl-containing resin can be controlled, and the performance stability of the carboxyl-containing resin can be maintained between manufacturing batches.

Claims

1. A method for manufacturing a carboxyl-containing resin, comprising the following steps: Step A involves reacting an epoxy compound (a) with an unsaturated monobasic acid (b) in an organic solvent to obtain a first liquid containing reaction product A. Step B involves adding water to the first liquid containing reaction product A, controlling the water content of the first liquid containing reaction product A to be between 0.1% by mass and 0.45% by mass, to obtain a second liquid containing reaction product A; and, In step C, a polybasic acid dianhydride (c) and a polybasic acid monohydric acid (d) are added to the second liquid containing reaction product A and reacted to obtain a carboxyl-containing resin. 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 the 1 equivalent of the polybasic acid monohydric anhydride (d).

2. The method for manufacturing carboxyl-containing resin according to claim 1, wherein, In step C, a polyol (e) is further added and reacted.

3. The method for manufacturing carboxyl-containing resin according to claim 2, wherein, The polyol (e) contains trimethylolpropane.

4. The method for manufacturing a carboxyl-containing resin according to claim 1, wherein, The polybasic acid dianhydride (c) includes biphenyltetracarboxylic acid dianhydride.

5. The method for manufacturing a carboxyl-containing resin according to claim 1, wherein, The polybasic acid monohydric anhydride (d) includes tetrahydrophthalic anhydride.

6. A method for manufacturing ink, wherein, The ink comprises (A) an alkali-soluble resin, an organic solvent, and (D) a colorant. The manufacturing method includes the following steps: mixing a carboxyl-containing resin manufactured by the manufacturing method according to any one of claims 1 to 5 as the (A) alkali-soluble resin.

7. A method for manufacturing a photosensitive resin composition, wherein, The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. The manufacturing method includes the following steps: mixing a carboxyl-containing resin manufactured by the manufacturing method according to any one of claims 1 to 5 as the (A) alkali-soluble resin.

8. The method for manufacturing the photosensitive resin composition according to claim 7, wherein, The photosensitive resin composition also includes (D) a colorant.

9. A method for manufacturing a cured material, comprising the step of curing a photosensitive resin composition obtained by the manufacturing method of claim 7 or 8.

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

11. A method for manufacturing an image display device, characterized in that, The cured product obtained by the manufacturing method of claim 9, or the black matrix obtained by the manufacturing method of claim 10.

12. A method for controlling the molecular weight of a carboxyl-containing resin, comprising the following steps: controlling the water content of a first liquid containing reaction product A, obtained by reacting an epoxy compound (a) with an unsaturated monocarboxylic acid (b) in an organic solvent, to a level where the water content is 0.1% by mass or more and 0.45% by mass or less, to obtain a second liquid containing reaction product A; adding a polybasic acid dianhydride (c), a polybasic acid monohydric acid (d), and a polyol (e) to the second liquid containing reaction product A and reacting them to obtain a carboxyl-containing resin. The amount of the polyol (e) is 0.01 equivalents or more and 1 equivalent or less relative to 1 equivalent of the unsaturated monocarboxylic acid (b).

13. The method for controlling the molecular weight of carboxyl-containing resin according to claim 12, wherein, Water is added to the first liquid containing reaction product A in such a way that the water content of the solution containing the second liquid containing reaction product A is 0.1% by mass or more and 0.45% by mass or less, and the water content of the first liquid containing reaction product A is controlled to obtain the second liquid containing reaction product A.

14. The method for controlling the molecular weight of carboxyl-containing resin according to claim 12, wherein, The polyol (e) contains trimethylolpropane.

15. The method for controlling the molecular weight of the carboxyl-containing resin according to claim 12 or 13, wherein, The polybasic acid dianhydride (c) includes biphenyltetracarboxylic acid dianhydride.

16. The method for controlling the molecular weight of the carboxyl-containing resin according to claim 12 or 13, wherein, The polybasic acid monohydric anhydride (d) includes tetrahydrophthalic anhydride.

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