Photosensitive resin composition, cured product, black matrix, and image display device

Abstract

Provided is a photosensitive resin composition from which a pattern having excellent light-blocking properties can be formed and which is prevented from the occurrence of foreign matters and unevenness. The photosensitive resin composition according to the present invention comprises (A) a pigment, (D) an alkali-soluble resin, (F) a photopolymerization initiator, and an organic solvent, in which the pigment (A) comprises carbon black (a1), the ratio of the total content of all of solid matters to the whole mass of the photosensitive resin composition is 15% by mass or less, the ratio of the content of the carbon black (a1) to the total content of all of the solid matters in the photosensitive resin composition is more than 40% by mass, and the average value of sedimentation rates at a transmittance of 10% of the photosensitive resin composition is 800 μm / h or less when measured by a centrifugal sedimentation method.

Description

Photosensitive resin composition, cured product, black matrix and image display device

[0001] The present invention relates to a photosensitive resin composition, a cured product, a black matrix, and an image display device. This application claims priority to Japanese Patent Application No. 2022-044594 filed on March 18, 2022, and Japanese Patent Application No. 2023-009336 filed on January 25, 2023, the contents of which are incorporated herein by reference.

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

[0003] Currently, a photolithography method using a photosensitive resin composition is known as a typical method for producing color filters. In the photolithography method, for example, a photosensitive resin composition containing an alkali-soluble resin is applied to a transparent substrate and dried to form a photosensitive resin film. The photosensitive resin film is exposed to light in a predetermined pattern, developed using an alkaline developer, and then cured by high-temperature treatment at 200°C or higher to form a pattern. When the photosensitive resin composition is used to form pixels, black matrices, etc. of a color filter, it contains a colorant. Pigments such as carbon black or dyes are used as the colorant (Patent Document 1).

[0004] Japanese Patent Application Publication No. 2012-68613

[0005] One of the important properties of a black matrix is ​​its light-shielding ability. Light-shielding ability can be improved by increasing the carbon black content in the solid content of the photosensitive resin composition. However, increasing the carbon black content increases the carbon black concentration in the photosensitive resin composition, reducing the dispersion stability of the carbon black and making it more likely for foreign matter, including carbon black aggregates, to form. Such foreign matter can cause serious functional defects in photosensitive resin films and patterns. Increasing the solid content in the photosensitive resin composition increases the viscosity of the photosensitive resin composition, improving the dispersion stability of the carbon black. However, this can easily cause unevenness in the film thickness of the resulting photosensitive resin film, and ultimately unevenness in color density (shade variations). Such shade variations can cause serious functional defects in photosensitive resin films and patterns.

[0006] Therefore, an object of the present invention is to provide a photosensitive resin composition that provides a pattern with excellent light-shielding properties and suppresses the occurrence of foreign matter and unevenness, and a cured product, black matrix, and image display device using the same.

[0007] The gist of the present invention resides in the following: [1] A photosensitive resin composition containing (A) a pigment, (D) an alkali-soluble resin, (F) a photopolymerization initiator, and an organic solvent, wherein the (A) pigment contains carbon black (a1), the photosensitive resin composition has a total solid content of 15% by mass or less relative to the total mass of the photosensitive resin composition, the carbon black (a1) has a content of more than 40% by mass relative to the total solid content of the photosensitive resin composition, and the photosensitive resin composition has an average sedimentation velocity at 10% transmittance measured by centrifugal sedimentation of 800 μm / h or less. [2] The photosensitive resin composition according to [1], wherein the carbon black (a1) has a dibutyl phthalate absorption of 55 mL / 100 g or more and 100 mL / 100 g or less. [3] The photosensitive resin composition according to [1] or [2], wherein the carbon black (a1) has an average primary particle diameter of 15 nm or more and 30 nm or less. [4] The specific surface area of ​​the carbon black (a1) measured by the BET method is 115 m ２ / g or less. [5] The photosensitive resin composition according to any one of [1] to [4], further containing a (B) dispersant. [6] The photosensitive resin composition according to [5], wherein the content ratio of the (A) pigment to the (B) dispersant ((A) pigment / (B) dispersant) on a mass basis is 6.5 or less. [7] The photosensitive resin composition according to any one of [1] to [6], further containing an (E) photopolymerizable compound. [8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7]. [9] A black matrix comprising the cured product according to [8].

[10] An image display device having the cured product according to

[16] .

[0008] According to the present invention, a photosensitive resin composition can be provided which has excellent light-shielding properties for the formed pattern and which suppresses the occurrence of foreign matter and unevenness.

[0009] 1 is a schematic cross-sectional view illustrating an example of an organic EL element according to the present invention.

[0010] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be practiced with various modifications within the scope of the gist thereof. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth)acrylate" and "(meth)acryloyl". In the present invention, the "total solids content" of a photosensitive resin composition means all components contained in the photosensitive resin composition other than the organic solvent and water. Even if a component other than the organic solvent and water is liquid at room temperature, that component is not included in the organic solvent and water, but is included in the total solids content. The same applies to the "total solids content" of a pigment dispersion.

[0011] In the present invention, the "average primary particle size" of carbon black is determined by a method of directly measuring the size of primary particles from an electron microscope photograph. Specifically, carbon black is observed under an electron microscope, and the minute spherical portions constituting primary aggregates (aggregates) are considered as single particles (primary particles). The diameters of 10 or more of these minute particulate portions are measured as a perfect circle approximation, and the average value thereof is defined as the average primary particle size. The same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM). In the present invention, the "dibutyl phthalate absorption" of carbon black is measured in accordance with JIS K 6217-4. Details are as described in the Examples below. Hereinafter, "dibutyl phthalate" is also referred to as "DBP." In the present invention, the "specific surface area measured by the BET method" of carbon black is measured in accordance with JIS K 6217-7. Details are as described in the Examples below. In the present invention, "weight average molecular weight" refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, unless otherwise specified, "amine value" refers to the amine value calculated in terms of effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant. The measurement method will be described later.

[0012] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention contains (A) a pigment, (D) an alkali-soluble resin, (F) a photopolymerization initiator, and an organic solvent.

[0013] <(A) Pigment> The (A) pigment contains carbon black (a1).

[0014] The average primary particle diameter of the carbon black (a1) is preferably 30 nm or less, more preferably 29 nm or less, even more preferably 27 nm or less, and preferably 15 nm or more, more preferably 18 nm or more, and even more preferably 20 nm or more. When the average primary particle diameter is equal to or less than the upper limit, the average 10% sedimentation velocity of the photosensitive resin composition tends to be small, and the effect of suppressing the generation of carbon black-derived foreign matter tends to be improved. When the average primary particle diameter is equal to or greater than the lower limit, the dispersion stability of the carbon black (a1) tends to be improved, and the viscosity stability of the photosensitive resin composition over time tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 15 nm or more and 30 nm or less, 18 nm or more and 29 nm or less, or 20 nm or more and 27 nm or less.

[0015] The DBP absorption of carbon black (a1) is preferably 55 mL / 100 g or more, more preferably 56 mL / 100 g or more, even more preferably 57 mL / 100 g or more, and preferably 100 mL / 100 g or less, more preferably 80 mL / 100 g or less, and even more preferably 70 mL / 100 g or less. When the DBP absorption is equal to or greater than the lower limit, the average 10% sedimentation velocity of the photosensitive resin composition tends to be smaller, and the effect of suppressing the generation of carbon black-derived foreign matter tends to be improved. When the DBP absorption is equal to or less than the upper limit, the light-shielding properties and curability of the coating film tend to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 55 mL / 100 g or more and 100 mL / 100 g or less, 56 mL / 100 g or more and 80 mL / 100 g or less, or 57 mL / 100 g or more and 70 mL / 100 g or less.

[0016] The specific surface area of ​​carbon black (a1) measured by the BET method is 115 m ２ / g or less is preferable, and 110m ２ / g or less is more preferable, and 105m ２ / g or less is more preferable, and ２ / g or more is preferable, and 60m ２ / g or more is more preferable, and 70m ２ / g or more is more preferable. If the specific surface area is equal to or less than the upper limit, the amount of dispersant required becomes appropriate, and the balance between dispersion stability, light-shielding properties of the coating film, and curability tends to be good. If the specific surface area is equal to or more than the lower limit, the average 10% sedimentation velocity of the photosensitive resin composition becomes small, and the effect of suppressing the generation of foreign matter derived from carbon black tends to be improved. The upper and lower limits can be arbitrarily combined. For example, 50 to 115 m ２ / g, and 60 to 110 m ２ / g, and 70 to 105 m ２ / g.

[0017] Examples of carbon black (a1) include the following carbon blacks: NEROX (registered trademark; the same applies hereinafter) 305, NEROX 505, NEROX 510, NEROX 555, PRINTEX (registered trademark; the same applies hereinafter) Nature, and PRINTEX 300, manufactured by Orion Engineered Carbons; RAVEN (registered trademark; the same applies hereinafter) 1080, manufactured by BIRLA CARBON; and MA7, MA11, MA100, MA100R, and MA100S, manufactured by Mitsubishi Chemical Corporation. Carbon black (a1) may be a mixture of multiple types of carbon black. When carbon black (a1) is a mixture of multiple types of carbon black, it is sufficient that the average primary particle size, DBP absorption, and specific surface area of ​​the mixture are each within the preferred ranges described above.

[0018] The pigment (A) may further contain other pigments besides carbon black (a1) as necessary. Examples of other pigments include pigments of various colors used as colorants for coloring photosensitive resin compositions. Examples of such pigments include blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments (excluding carbon black (a1)). These pigments may be organic or inorganic. The structure of the organic pigment is not particularly limited, and examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments.

[0019] Specific examples of other pigments are shown below by pigment number. Note that the terms "C.I. Pigment Red 2" and the like below refer to the Color Index (C.I.). Examples of red pigments include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1 , 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 1 66, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 2 35, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Preferred are C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferred are C.I. Pigment Red 177, 209, 224, 254.

[0020] Examples of blue pigments include C.I. 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. C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and C.I. Pigment Blue 15:6 and 60 are more preferred.

[0021] Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Preferred are C.I. Pigment Green 7, 36, and 58.

[0022] Examples of yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 are preferably mentioned. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. Pigment Yellow 83, 138, 139, 150, 180.

[0023] Examples of orange pigments include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Preferably, C.I. Pigment Orange 38, 64, and 71 are used.

[0024] Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. C.I. Pigment Violet 19, 23, and 29 are preferred, and C.I. Pigment Violet 23 and 29 are more preferred.

[0025] As the black pigment, a pigment that exhibits black color by mixing multiple colored pigments (for example, three colors of red, green, and blue) may be used, or a pigment that exhibits black color may be used alone, or these may be used in combination.

[0026] Examples of pigments that can be mixed to prepare black pigments include Victoria Pure Blue (42595), Auramine O (41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), Rhodamine B (45170), Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimler Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Firstgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), and Lionol Green 2YS (Pigment Green 36). The numbers in parentheses above refer to the Color Index (C.I.).

[0027] Further, other pigments that can be mixed and used are shown by C.I. number, for example, C.I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. Examples of suitable pigments include C.I. Blue Pigments 15, 15:1, 15:4, 22, 60, and 64, C.I. Green Pigment 7, and C.I. Brown Pigments 23, 25, and 26.

[0028] Examples of black pigments that can be used alone include lamp black, bone black, graphite, iron oxide black pigments (iron black, etc.), aniline black, cyanine black, titanium black, perylene black, and lactam black.

[0029] Other pigments that can be used include, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

[0030] A plurality of these pigments can also be used in combination. For example, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination to adjust the chromaticity.

[0031] The content of the (A) pigment relative to the total solid content of the photosensitive resin composition of the present invention is preferably greater than 40% by mass, more preferably 45% by mass or greater, even more preferably 50% by mass or greater, and preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the content of the (A) pigment is equal to or greater than the above-mentioned lower limit, the light-blocking properties of the cured product (pattern, etc.) of the photosensitive resin composition are excellent. When the content of the (A) pigment is equal to or less than the above-mentioned upper limit, the effect of suppressing the generation of foreign matter tends to be better. The above upper and lower limits can be arbitrarily combined. For example, the content may be greater than 40% by mass but not greater than 65% by mass, 45 to 60% by mass, or 50 to 55% by mass.

[0032] The content of carbon black (a1) relative to the total solid content of the photosensitive resin composition of the present invention is greater than 40% by mass, preferably 45% by mass or more, more preferably 50% by mass or more, and preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the content of carbon black (a1) is equal to or greater than the above-mentioned lower limit, the light-shielding properties of the cured product (pattern, etc.) of the photosensitive resin composition are excellent. When the content of carbon black (a1) is equal to or less than the above-mentioned upper limit, the effect of suppressing the generation of foreign matter tends to be more excellent. The above upper and lower limits can be arbitrarily combined. For example, it may be greater than 40% by mass but not greater than 65% by mass, 45 to 60% by mass, or 50 to 55% by mass.

[0033] The content of carbon black (a1) relative to the total mass of the pigment (A) is preferably 90 mass% or more, more preferably 95 mass% or more, and even more preferably 99 mass% or more, and may be 100 mass%.

[0034] <(B) Dispersant> The photosensitive resin composition of the present invention may contain a (B) dispersant. The (B) dispersant finely disperses the (A) pigment and stabilizes the dispersed state. As the (B) dispersant, a polymer dispersant having a functional group is preferred. Furthermore, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as a carboxy group; a phosphate group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferred. A polymer dispersant having a basic functional group such as a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is particularly preferred. The use of such a polymer dispersant having a basic functional group tends to improve dispersibility.

[0035] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants.

[0036] Examples of dispersants include, by trade name, EFKA (registered trademark, manufactured by EFKA Chemicals BV), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW or FLOLENE (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Inc.). These polymer dispersants may be used alone or in combination of two or more.

[0037] In terms of adhesion and linearity, the dispersant is preferably a urethane-based polymer dispersant and / or an acrylic-based polymer dispersant having a basic functional group, and a urethane-based polymer dispersant is more preferred in terms of adhesion. In another embodiment, in terms of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester and / or polyether bond is preferred.

[0038] The weight-average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. By setting the Mw at or below the upper limit, alkaline developability tends to be good even when the pigment concentration is high. The upper and lower limits can be combined in any manner. For example, it may be 700 to 100,000, 700 to 50,000, or 1,000 to 30,000.

[0039] Examples of urethane-based or acrylic polymer dispersants include the DISPERBYK 160 to 167 and 182 series (all urethane-based), and DISPERBYK 2000 and 2001 (all acrylic-based) (all manufactured by BYK-Chemie). Particularly preferred examples of the above-mentioned urethane-based polymer dispersants having a basic functional group and a polyester and / or polyether bond and a weight-average molecular weight of 30,000 or less include DISPERBYK 167 and 182.

[0040] Examples of urethane-based polymer dispersants include dispersion resins having a weight-average molecular weight of 1,000 to 200,000, which are obtained by reacting a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and a number-average molecular weight of 300 to 10,000, and a compound having an active hydrogen and a tertiary amino group in the same molecule.

[0041] Examples of polyisocyanate compounds include aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), ω,ω'-diisocyanate dimethyl cycloisocyanate; Examples of suitable polyisocyanates include alicyclic diisocyanates such as hexane; aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate; triisocyanates such as lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), and tris(isocyanatophenyl)thiophosphate, as well as trimers, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, with trimers of tolylene diisocyanate and trimers of isophorone diisocyanate being more preferred. These may be used alone or in combination of two or more.

[0042] Examples of methods for producing an isocyanate trimer include a method in which a polyisocyanate compound is subjected to partial trimerization of the isocyanate groups using an appropriate trimerization catalyst, such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, or a carboxylate, and the trimerization is terminated by adding a catalyst poison. Thereafter, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

[0043] Examples of compounds having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0044] Examples of polyether glycols include polyether diols and polyether ester diols, including compounds obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol.

[0045] Examples of polyetherester diols include those obtained by reacting an ether group-containing diol or a mixture thereof with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, such as poly(polyoxytetramethylene) adipate. Preferred polyether glycols include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0046] Examples of polyester glycols include dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof, and glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, Examples of suitable polyester glycols include compounds obtained by polycondensation of aliphatic glycols such as 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and N-alkyldialkanolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate, as well as polylactone diols or polylactone monools obtained using glycols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol and polymethylvalerolactone. Polycaprolactone glycol and polycaprolactones using alcohols having 1 to 25 carbon atoms as initiators are preferred.

[0047] Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.

[0048] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is preferably 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000. In the compound having active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, i.e., the hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom, includes hydrogen atoms in functional groups such as hydroxyl groups, amino groups, and thiol groups, and among these, the hydrogen atom of an amino group, particularly a primary amino group, is preferred.

[0049] Examples of the tertiary amino group in a compound having active hydrogen and a tertiary amino group in the same molecule include an amino group having an alkyl group having 1 to 4 carbon atoms, and heterocyclic structures such as an imidazole ring and a triazole ring. Examples of compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0050] When the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include a 5-membered nitrogen-containing heterocyclic ring such as a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, and a benzothiadiazole ring; and a 6-membered nitrogen-containing heterocyclic ring such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, and an isoquinoline ring, with an imidazole ring and a triazole ring being preferred.

[0051] Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. 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. Preferred compounds having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole. These may be used alone or in combination of two or more.

[0052] The preferred blending ratio of raw materials when producing a urethane-based polymer dispersant is 100 parts by mass of polyisocyanate compound, 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule. The above blending ratios can be combined as desired. For example, per 100 parts by mass of polyisocyanate compound, 10 to 200 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule are preferred; per 100 parts by mass of polyisocyanate compound, 20 to 190 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule are more preferred; per 100 parts by mass of polyisocyanate compound, 30 to 180 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.3 to 24 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule are even more preferred.

[0053] The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Examples of solvents used in the production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; alcohols such as diacetone alcohol, isopropanol, sec-butanol, and tert-butanol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

[0054] In producing the urethane-based polymer dispersant, a urethane-forming reaction catalyst may be used. Examples of the urethane-forming reaction catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0055] The amount of the compound having an active hydrogen and a tertiary amino group introduced in the same molecule is preferably controlled to an amine value after the reaction of 1 to 100 mgKOH / g, more preferably 5 to 95 mgKOH / g. By controlling the amine value to be equal to or greater than the lower limit, dispersibility tends to be improved. On the other hand, by controlling the amine value to be equal to or less than the upper limit, developability tends to be improved.

[0056] The amine value is expressed as the mass of KOH equivalent to the amount of base per 1 g of solids in the sample excluding the solvent, and can be measured by the following method. 0.5 to 1.5 g of the sample is accurately weighed into a 100 mL beaker and dissolved in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is diluted to 0.1 mol / L HClO. ４ Neutralization titration is performed with a (perchloric acid) acetic acid solution. The inflection point of the titration pH curve is set as the titration endpoint, and the amine value is calculated using the following formula: Amine value [mg KOH / g] = (561 x V) / (W x S) (where W is the weight of the dispersant sample [g], V is the titration amount at the titration endpoint [mL], and S is the solids concentration [mass %] of the dispersant sample.)

[0057] When isocyanate groups remain in the polymer dispersant, it is preferable to consume the isocyanate groups with an alcohol or an amino compound, since this increases the stability of the product over time.

[0058] The weight-average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. An upper limit of 30,000 or less is particularly preferred. When the Mw is equal to or greater than the lower limit, dispersibility and dispersion stability tend to be improved, while when the Mw is equal to or less than the upper limit, solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the Mw may be 1,000 to 30,000, 2,000 to 30,000, or 3,000 to 30,000. In particular, when the Mw is 30,000 or less, alkaline developability tends to be improved, even when the pigment concentration is particularly high. Examples of commercially available urethane dispersants include DISPERBYK 167 and 182 (BYK-Chemie).

[0059] When the photosensitive resin composition of the present invention contains a (B) dispersant, the content of the (B) dispersant relative to the total solids content of the photosensitive resin composition of the present invention is preferably 3% by mass or more, more preferably 4.5% by mass or more, even more preferably 6% by mass or more, and preferably 15% by mass or less, more preferably 13.5% by mass or less, and even more preferably 12% by mass or less. When the content of the (B) dispersant is equal to or greater than the above-mentioned lower limit, the dispersion stability of the pigment tends to be improved, and the average 10% sedimentation velocity of the photosensitive resin composition tends to be smaller. When the content of the (B) dispersant is equal to or less than the above-mentioned upper limit, the developability in an alkaline developer tends to be better. The above upper and lower limits can be arbitrarily combined. For example, it may be 3 to 12% by mass, 4.5 to 13.5% by mass, or 6 to 15% by mass.

[0060] When the photosensitive resin composition of the present invention contains a (B) dispersant, the mass ratio of the (A) pigment to the (B) dispersant ((A) pigment / (B) dispersant) is preferably 6.5 or less, more preferably 6.0 or less, and even more preferably 5.5 or less, and is preferably 4.0 or more, more preferably 4.5 or more, and even more preferably 5.0 or more. When the (A) pigment / (B) dispersant ratio is equal to or less than the upper limit, the dispersion stability of the (A) pigment tends to be improved, and the average 10% sedimentation velocity of the photosensitive resin composition tends to be smaller. When the (A) pigment / (B) dispersant ratio is equal to or greater than the lower limit, the developable solubility tends to be better. The upper and lower limits can be arbitrarily combined. For example, it may be 4.0 to 6.5, 4.5 to 6.0, or 5.0 to 5.5.

[0061] When the photosensitive resin composition of the present invention contains a dispersant (B), the mass ratio of the carbon black (a1) to the dispersant (B) (carbon black (a1) / dispersant (B)) is preferably 6.5 or less, more preferably 6.0 or less, and even more preferably 5.5 or less, and is preferably 4.0 or more, more preferably 4.5 or more, and even more preferably 5.0 or more. When the carbon black (a1) / dispersant (B) ratio is equal to or less than the upper limit, the dispersion stability of the carbon black (a1) tends to be improved, and the average 10% sedimentation velocity of the photosensitive resin composition tends to be smaller. When the carbon black (a1) / dispersant (B) ratio is equal to or greater than the lower limit, the developability tends to be better. The upper and lower limits can be arbitrarily combined. For example, the ratio may be 4.0 to 6.5, 4.5 to 6.0, or 5.0 to 5.5.

[0062] <(C) Dispersing Aid> The photosensitive resin composition of the present invention may contain a dispersing aid (C) to improve the dispersion stability of the pigment (A). Examples of the dispersing aid (C) include pigment derivatives. Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinophthalone-based derivatives being preferred.

[0063] Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc., which are bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., and are preferably a sulfonic acid group. Furthermore, a single pigment skeleton may be substituted with a plurality of these substituents. Examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0064] When the photosensitive resin composition of the present invention contains a dispersing aid (C), the content of the dispersing aid (C) relative to the total solids content of the photosensitive resin composition of the present invention is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, even more preferably 0.6% by mass or more, and preferably 2.5% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.1% by mass or less. When the content of the dispersing aid (C) is equal to or greater than the above-mentioned lower limit, the dispersion stability tends to be better. When the content of the dispersing aid (C) is equal to or less than the above-mentioned upper limit, the developability tends to be stable and the substrate adhesion tends to be good. The above upper and lower limits can be arbitrarily combined. For example, the content may be 0.2 to 2.5% by mass, 0.4 to 1.8% by mass, or 0.6 to 1.1% by mass.

[0065] When the photosensitive resin composition of the present invention contains a dispersing aid (C), the mass ratio of the pigment (A) to the dispersing aid (C) ((A) pigment / (C) dispersing aid) is preferably 10 or more, more preferably 25 or more, and even more preferably 50 or more, and is preferably 200 or less, more preferably 100 or less, and even more preferably 75 or less. When the ratio of pigment (A) to dispersing aid (C) is equal to or greater than the lower limit, developability tends to be stable and substrate adhesion tends to be better, while when it is equal to or less than the upper limit, dispersion stability tends to be better. The upper and lower limits can be arbitrarily combined. For example, it may be 10 to 200, 25 to 100, or 50 to 75.

[0066] When the photosensitive resin composition of the present invention contains a dispersing aid (C), the mass ratio of the carbon black (a1) to the dispersing aid (C) (carbon black (a1) / dispersing aid (C)) is preferably 10 or more, more preferably 25 or more, and even more preferably 50 or more, and is preferably 200 or less, more preferably 100 or less, and even more preferably 75 or less. When the carbon black (a1) / dispersing aid (C) ratio is equal to or greater than the above-mentioned lower limit, developability tends to be stable and substrate adhesion tends to be better, while when it is equal to or less than the above-mentioned upper limit, dispersion stability tends to be better. The above upper and lower limits can be arbitrarily combined. For example, it may be 10 to 200, 25 to 100, or 50 to 75.

[0067] <(D) Alkali-Soluble Resin> The alkali-soluble resin (D) is not particularly limited as long as it is an alkali-soluble resin, and examples thereof include resins containing a carboxy group or a hydroxyl group. More specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxy-containing epoxy resins, carboxy-containing urethane resins, novolac resins, and polyvinylphenol resins. In particular, (D1) epoxy (meth)acrylate resins and (D2) acrylic copolymer resins are preferably used from the viewpoint of excellent plate-making properties. These resins can be used alone or in combination of two or more.

[0068] <(D1) Epoxy (meth)acrylate Resin> The (D1) epoxy (meth)acrylate resin is a resin obtained by reacting an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxy group in the ester moiety to generate hydroxyl groups, and then reacting the resulting hydroxyl groups with a compound having two or more substituents capable of reacting with hydroxyl groups, such as a polybasic acid and / or anhydride thereof. The (D1) epoxy (meth)acrylate resin also includes a resin obtained by reacting a compound having two or more substituents capable of reacting with hydroxyl groups with the polybasic acid and / or anhydride thereof prior to reacting the hydroxyl groups with the polybasic acid and / or anhydride thereof, followed by the polybasic acid and / or anhydride thereof. The (D1) epoxy (meth)acrylate resin also includes a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl groups of the resin obtained by the above reaction. Epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure, and are not limited to "(meth)acrylates." However, since epoxy compounds (epoxy resins) are used as raw materials and "(meth)acrylates" are a representative example, they are named as such according to convention.

[0069] As the epoxy (meth)acrylate resin (D1), an epoxy (meth)acrylate resin (D1-1) and / or an epoxy (meth)acrylate resin (D1-2) (hereinafter sometimes referred to as a "carboxy group-containing epoxy (meth)acrylate resin") are preferably used from the viewpoint of developability and reliability. As the epoxy (meth)acrylate resin (D1), those having an aromatic ring in the main chain are more preferably used from the viewpoint of outgassing.

[0070] <Epoxy (meth)acrylate resin (D1-1)> An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting with a polybasic acid and / or an anhydride thereof. <Epoxy (meth)acrylate resin (D1-2)> An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

[0071] Here, the term "epoxy resin" refers to raw material compounds before they are thermoset to form a resin, and the epoxy resin can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epihalohydrin. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer. Suitable types of epoxy resins used as raw materials include cresol novolac epoxy resins, phenol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, trisphenolmethane epoxy resins, biphenyl novolac epoxy resins, naphthalene novolac epoxy resins, epoxy resins that are the reaction products of a polyaddition reaction product of dicyclopentadiene with phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resins, and fluorene epoxy resins. Those having an aromatic ring in the main chain are more preferred.

[0072] Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004" manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76°C)), and bisphenol F type resins (e.g., "jER 807, "EP-4001", "EP-4002", "EP-4004", etc.), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 350, softening point: 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN" manufactured by Nippon Kayaku Co., Ltd.), -201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by Dow Chemical Company, "DEN-438" manufactured by Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (for example, "EOCN (registered trademark, the same applies hereinafter)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd.), Suitable epoxy resins that can be used include epoxy resins represented by the following general formulas (B1) to (B4): epoxy resins represented by the following general formulas (B1) to (B4)Specific examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1); "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2); "E-201" manufactured by Osaka Organic Chemical Industry Ltd. as an epoxy resin represented by the following general formula (B3); and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

[0073]

[0074] In formula (B1), a is an average value and represents a number from 0 to 10; １１１ Each of R independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. １１１ may be the same or different.

[0075]

[0076] In formula (B2), b1 and b2 each independently represent an average value and a number from 0 to 10; １２１ Each of R independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. １２１ may be the same or different.

[0077]

[0078] In formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), provided that the molecular structure contains one or more adamantane structures. c represents 2 or 3.

[0079]

[0080] In formulas (B3-1) and (B3-2), R １３１ ~R １３４ and R １３５ ~R １３７each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0081]

[0082] In formula (B4), p and q each independently represent an integer of 0 to 4; １４１ and R １４２ each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom; R １４３ and R １４４ each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or greater.

[0083] As the epoxy resin, it is preferable to use an epoxy resin represented by any one of formulas (B1) to (B4).

[0084] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetrahydrophthalate, 2-(meth)acryloyloxyethyl methyl esters. Examples of suitable acrylic acid dimers include 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalate, 2-(meth)acryloyloxybutyl phthalate, 2-(meth)acryloyloxybutyl maleate (meth), and monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid; or monomers obtained by adding acids (anhydrides) such as succinic acid anhydride, phthalic acid anhydride, and maleic acid anhydride to hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; and (meth)acrylic acid dimers. Among these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0085] Known methods can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150° C. Examples of esterification catalysts that can be used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0086] The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may each be used singly or in combination of two or more. The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group used is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, per equivalent of the epoxy group in the epoxy resin. By using an amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group that is equal to or greater than the lower limit, the introduction of an insufficient amount of unsaturated groups can be prevented, and the subsequent reaction with the polybasic acid and / or its anhydride tends to be sufficient. By using an amount equal to or less than the upper limit, the amount of unreacted α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group can be prevented, and good curing properties tend to be obtained.

[0087] Examples of polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic acid dianhydride.

[0088] The addition reaction of a polybasic acid and / or anhydride thereof can be carried out using known techniques, and the target product can be obtained by continuing the reaction under conditions similar to those of the addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. The amount of polybasic acid and / or anhydride thereof added is preferably such that the acid value of the resulting carboxy-containing epoxy (meth)acrylate resin is 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g. By adjusting the amount to be equal to or greater than the lower limit, alkaline developability tends to be improved. By adjusting the amount to be equal to or less than the upper limit, curing performance tends to be improved.

[0089] During the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol may be added to introduce a multi-branched structure. In this case, there are no particular restrictions on the order of mixing the polybasic acid and / or its anhydride with the polyfunctional alcohol. By heating, the polybasic acid and / or its anhydride undergoes an addition reaction with any hydroxyl group present in the mixture of the reaction product of the epoxy resin with an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol.

[0090] The use of a polyhydric alcohol increases the molecular weight of the epoxy (meth)acrylate resin (D1), allows for the introduction of branching into the molecule, and tends to balance the molecular weight and viscosity. In addition, the introduction rate of acid groups into the molecule can be increased, which tends to make it easier to balance sensitivity, adhesion, and the like.

[0091] In addition to the above-mentioned carboxyl group-containing epoxy (meth)acrylate resins, for example, those described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.

[0092] The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, especially preferably 4,000 or more, and particularly preferably 5,000 or more. It is also preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. By setting the Mw at or above the lower limit, excessive solubility in the developer tends to be suppressed. By setting the Mw at or below the upper limit, solubility in the developer tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1,000 to 30,000, 1,500 to 20,000, 1,500 to 15,000, or 2,000 to 15,000.

[0093] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting the acid value at or above the lower limit, the development solubility tends to be improved and the resolution tends to be good. By setting the acid value at or below the upper limit, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 130 mgKOH / g.

[0094] The chemical structure of the epoxy(meth)acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, it is preferable to contain an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (d1-I) (hereinafter may be abbreviated as "(d1-I) epoxy(meth)acrylate resin") and / or an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (d1-II) (hereinafter may be abbreviated as "(d1-II) epoxy(meth)acrylate resin"):

[0095]

[0096] In formula (d1-I), R １１ represents a hydrogen atom or a methyl group, R １２ represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (d1-I) may be further substituted with any substituent.

[0097]

[0098] In formula (d1-II), R １３ each independently represents a hydrogen atom or a methyl group; R １４ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R １５ and R １６ each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0099] <(d1-I) Epoxy (meth)acrylate resin>

[0100]

[0101] In formula (d1-I), R １１ represents a hydrogen atom or a methyl group, R １２ represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (d1-I) may be further substituted with any substituent.

[0102] (R １２ In the formula (d1-I), R１２ represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.

[0103] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, from the viewpoint of reducing penetration of the developer into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, 20 or less is preferred, more preferably 15 or less, and even more preferably 10 or less. By setting the carbon number at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 1 to 15, or 1 to 10.

[0104] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeleton rigidity, a methylene group is preferred. Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic groups have, as side chains, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 12 or less, more preferably 10 or less. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be improved. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 12, 1 to 10, or 2 to 10. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, dicyclopentadiene, or dicyclopentane. From the viewpoint of skeletal rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0105] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0106] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be obtained, surface roughness during development tends to be less likely to occur, and adhesion to the substrate tends to be good. By setting the number of carbon atoms at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 20, 5 to 15, or 6 to 10.

[0107] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furopyrrole rings, furofuran rings, thienofuran rings, benzisoxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinnoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, each having two free valences. From the viewpoint of patterning properties, a benzene ring or naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0108] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, it is preferably unsubstituted.

[0109] Examples of the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include a group linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably one or more, more preferably two or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the content at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the content at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3.

[0110] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups represented by the following formulae (d1-IA) to (d1-IF). From the viewpoints of the rigidity of the skeleton and the hydrophobicity of the film, the group represented by the following formula (d1-IA) is preferred.

[0111]

[0112] In formula (d1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. Furthermore, the epoxy (meth)acrylate (d1-I) may contain both a partial structure in which k is 1 and a partial structure in which k is 2.

[0113] The benzene ring in formula (d1-I) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of patterning properties, it is preferably unsubstituted.

[0114] From the viewpoint of ease of synthesis, the partial structure represented by formula (d1-I) is preferably a partial structure represented by the following general formula (d1-I-1).

[0115]

[0116] In formula (d1-I-1), R １１ , R １２ and k have the same meaning as in formula (d1-I), and R Ｘ represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (d1-I-1) may be further substituted with any substituent.

[0117] The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0118] The benzene ring in formula (d1-I-1) may be further substituted with any substituent. As the substituent, those exemplified for the benzene ring in formula (d1-I) can be preferably used.

[0119] (d1-I) The partial structure represented by formula (d1-I-1) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types, and for example, R Ｘ is a hydrogen atom, and R Ｘ However, polybasic acid residues may be present in the mixture.

[0120] The number of partial structures represented by formula (d1-I) contained in one molecule of the epoxy (meth)acrylate resin (d1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Also, it is preferably 20 or less, and even more preferably 15 or less. By making the number equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By making the number equal to or less than the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 1 to 15, or 3 to 15.

[0121] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (d1-I) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and most preferably 5,000 or more. It is also preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. By setting it to the lower limit or more, the residual film rate of the photosensitive resin composition tends to be good. By setting it to the upper limit or less, the solubility in the developer tends to be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 1,000 to 30,000, 1,500 to 2,000, 1,500 to 15,000, or 2,000 to 1,500.

[0122] The acid value of the (d1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting the acid value at or above the lower limit, the development solubility tends to be improved and the resolution tends to be good. By setting the acid value at or below the upper limit, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 130 mgKOH / g.

[0123] Specific examples of (d1-I) epoxy (meth)acrylate resins are listed below, where * indicates a bond.

[0124]

[0125]

[0126]

[0127]

[0128] <(d1-II) Epoxy (meth)acrylate resin>

[0129]

[0130] In formula (d1-II), R １３ each independently represents a hydrogen atom or a methyl group; R １４ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R １５ and R １６ each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0131] (R １４In formula (d1-II), R １４ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

[0132] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is also preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be more easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be more easily suppressed, and resolution tends to be improved. The upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 4 to 30, 6 to 20, or 8 to 15. Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of the film remaining rate and resolution of the photosensitive resin composition, an adamantane ring is preferred.

[0133] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. It is also preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, 1 to 5, 1 to 4, 2 to 4, or 3 to 4. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting the molecular weight at or above the lower limit, a strong film is easily obtained, and surface roughness during development tends to be less likely to occur. By setting the molecular weight at or below the upper limit, patterning properties tend to be good. The upper and lower limits can be arbitrarily combined. For example, the molecular weight may be 4 to 40, 6 to 40, 8 to 30, 10 to 20, or 12 to 15. Examples of aromatic rings in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. From the viewpoint of patterning properties, a fluorene ring is preferred.

[0134] The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.

[0135] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, 25 or less is preferred, more preferably 20 or less, and even more preferably 15 or less. By setting the carbon atom number at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 25, 3 to 20, or 6 to 15.

[0136] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeletal rigidity, a methylene group is preferred. Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic groups have, as side chains, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be improved. Also, by setting the number at or below the upper limit, deterioration in sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of skeleton rigidity, groups in which two hydrogen atoms have been removed from an adamantane ring are preferred.

[0137] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0138] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is also preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the carbon atom number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development tends to be less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 30, 5 to 20, or 6 to 15.

[0139] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furopyrrole rings, furofuran rings, thienofuran rings, benzisoxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinnoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, each having two free valences. From the viewpoint of patterning properties, a benzene ring or naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0140] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, it is preferably unsubstituted.

[0141] Examples of the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include a group linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably one or more, more preferably two or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the content at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the content at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3.

[0142] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the above-mentioned formulas (d1-IA) to (d1-IF). From the viewpoints of the rigidity of the skeleton and the hydrophobicity of the film, the group represented by formula (d1-IC) is preferred.

[0143] The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic group or aromatic ring group is substituted with the cyclic hydrocarbon group as a side chain, and a mode in which one carbon atom of an aliphatic group is included to form the cyclic hydrocarbon group as a side chain.

[0144] (R １５ , R １６ In formula (d1-II), R １５ and R１６ each independently represents a divalent aliphatic group which may have a substituent.

[0145] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, 20 or less is preferred, more preferably 15 or less, and even more preferably 10 or less. By setting the carbon atom number at or above the lower limit, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 3 to 15, or 6 to 10.

[0146] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeleton rigidity, a methylene group is preferred. Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic groups have, as side chains, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 12 or less, more preferably 10 or less. By setting the number at or above the lower limit, a strong film tends to be formed and substrate adhesion tends to be improved. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 12, or 2 to 10. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of skeletal rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring or an adamantane ring are preferred.

[0147] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0148] (m, n) In formula (d1-II), m and n each independently represent an integer of 0 to 2. By making m or n equal to or greater than the lower limit, patterning suitability becomes good and surface roughness that occurs during development tends to be less likely to occur, while by making m or n equal to or less than the upper limit, developability tends to be good. From the viewpoint of developability, m and n are preferably 0. From the viewpoint of patterning suitability and suppressing surface roughness that occurs during development, m and n are preferably 1 or greater.

[0149] The partial structure represented by formula (d1-II) is preferably a partial structure represented by the following general formula (d1-II-1) from the viewpoint of adhesion to a substrate.

[0150]

[0151] In formula (d1-II-1), R １３ , R １５ , R １６ , m and n are defined as in formula (d1-II), and R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or greater, and * represents a bond. The benzene ring in formula (d1-II-1) may be further substituted with any substituent.

[0152] (R α In formula (d1-II-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent. Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

[0153] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is also preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 6, 1 to 4, 1 to 3, or 2 to 3. The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 4 to 30, 6 to 20, or 8 to 15. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.

[0154] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and more preferably 3 or more. Furthermore, it is preferably 10 or less, and more preferably 5 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 2 to 5, or 3 to 5. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Furthermore, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 30, 5 to 20, or 6 to 15. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of developer solubility, a fluorene ring is preferred.

[0155] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0156] p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. By making p equal to or greater than the lower limit, the film hardness and film remaining rate tend to be good. By making p equal to or less than the upper limit, the developability tends to be good.

[0157] From the viewpoint of strong film hardness, Rα is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

[0158] The benzene ring in formula (d1-II-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of patterning properties, it is preferably unsubstituted.

[0159] Specific examples of the partial structure represented by formula (d1-II-1) are shown below.

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] The partial structure represented by formula (d1-II) is preferably a partial structure represented by the following general formula (d1-II-2) from the viewpoints of skeleton rigidity and film hydrophobicity.

[0166]

[0167] In formula (d1-II-2), R １３ , R １５ , R １６ , m and n are defined as in formula (d1-II), and R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond. The benzene ring in formula (d1-II-2) may be further substituted with any substituent.

[0168] (R β In formula (d1-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

[0169] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be more easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, or 2 to 5. The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Furthermore, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. By setting the number at or above the lower limit, roughness of the film surface during development tends to be more likely to be suppressed. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be more easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 4 to 40, 6 to 35, or 8 to 30. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of film loss during development and resolution, an adamantane ring is preferred.

[0170] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. It is also preferably 10 or less, and more preferably 5 or less. By setting the number at or above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss tend to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 2 to 5, or 3 to 5. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting the number at or above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to be equal to or less than the upper limit, deterioration in sensitivity and film loss can be easily suppressed, and resolution tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the value may be 4 to 40, 6 to 30, 8 to 20, or 10 to 15. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of developability, a fluorene ring is preferred.

[0171] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0172] From the viewpoint of suppressing film loss and resolution, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. βis preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0173] The benzene ring in formula (d1-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. In addition, the two benzene rings in formula (d1-II-2) are R β In addition, they may be linked via a substituent to form a tricyclic structure. In this case, the substituent may be —O—, —S—, —NH—, —CH ２ For example, the formation of a tricyclic structure by linking via —O— includes a divalent group such as R on each benzene ring. β This means that carbon atoms at the ortho positions of the carbon atom bonded to the xanthene skeleton are linked via —O— to form a xanthene skeleton. From the viewpoint of patterning properties, it is preferably unsubstituted. Furthermore, from the viewpoint of preventing film loss and the like, it is preferably substituted with a methyl group.

[0174] Specific examples of the partial structure represented by formula (d1-II-2) are shown below. In the examples, * indicates a bond.

[0175]

[0176]

[0177]

[0178]

[0179] The partial structure represented by formula (d1-II) is preferably a partial structure represented by the following general formula (d1-II-3) from the viewpoint of the coating film remaining rate and patterning properties.

[0180]

[0181] In formula (d1-II-3), R １３ , R １４ , R １５ , R １６, m and n are defined as in formula (d1-II), and R Ｚ represents a hydrogen atom or a polybasic acid residue.

[0182] The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. Ｚ That is, R Ｚ A plurality of Formula (d1-II-3) may be linked via an intermediate. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0183] (d1-II) The partial structure represented by formula (d1-II-3) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types, and for example, R Ｚ is a hydrogen atom, and R Ｚ However, polybasic acid residues may be present in the mixture.

[0184] The number of partial structures represented by formula (d1-II) contained in one molecule of the epoxy (meth)acrylate resin (d1-II) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By making the number equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By making the number equal to or less than the upper limit, deterioration in sensitivity and film loss tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 1 to 15, or 3 to 10.

[0185] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (d1-II) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and particularly preferably 5,000 or more. Also, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. By setting it to the lower limit or more, the residual film rate of the photosensitive resin composition tends to be good. By setting it to the upper limit or less, the solubility in the developer tends to be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 1,000 to 10,000, 1,500 to 10,000, 1,500 to 8,000, 2,000 to 8,000, or 2,000 to 7,000.

[0186] The acid value of the (d1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting the acid value at or above the lower limit, the development solubility tends to be improved and the resolution tends to be good. By setting the acid value at or below the upper limit, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 120 mgKOH / g.

[0187] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more resins. Furthermore, a portion of the carboxyl group-containing epoxy (meth)acrylate resin may be replaced with another binder resin. That is, the carboxyl group-containing epoxy (meth)acrylate resin may be used in combination with another binder resin. In this case, the proportion of the carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, and may be 100% by mass or less.

[0188] <(D2) Acrylic Copolymer Resin> From the viewpoint of compatibility with pigments, dispersants, and the like, it is preferable to use an acrylic copolymer resin (D2) as the alkali-soluble resin (D), and those described in JP 2014-137466 A can be preferably used.

[0189] Examples of the acrylic copolymer resin (D2) include copolymers of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (d2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (d2-2)").

[0190] Examples of the unsaturated monomer (d2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl]esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid. These unsaturated monomers (d2-1) can be used alone or in combination of two or more.

[0191] Examples of the unsaturated monomer (d2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0] ２，６] (meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ２，６ vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; and macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. These unsaturated monomers (d2-2) can be used alone or in combination of two or more.

[0192] In the copolymer of the unsaturated monomer (d2-1) and the unsaturated monomer (d2-2), the copolymerization ratio of the unsaturated monomer (d2-1) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (d2-1) in such a range, a photosensitive resin composition excellent in alkali developability and storage stability tends to be obtained.

[0193] Examples of the copolymer of the unsaturated monomer (d2-1) and the unsaturated monomer (d2-2) include the copolymers disclosed in Japanese Patent Application Laid-Open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728. The copolymer of the unsaturated monomer (d2-1) and the unsaturated monomer (d2-2) can be produced by a known method. For example, the structure, Mw, and Mw / Mn (Mn is the number average molecular weight) can be controlled by the methods disclosed in JP-A-2003-222717, JP-A-2006-259680, and WO 2007 / 029871.

[0194] Resins described in WO 2016 / 194619 and WO 2017 / 154439 may also be used.

[0195] The content of the alkali-soluble resin (D) relative to the total solids content of the photosensitive resin composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and is preferably less than 45% by mass, more preferably 40% by mass or less, and even more preferably 35% by mass or less. When the content of the alkali-soluble resin (D) is equal to or greater than the above-mentioned lower limit, the alkali development solubility of the unexposed areas tends to be superior. When the content is equal to or less than the above-mentioned upper limit, the alkali dissolution time of the unexposed areas tends to be appropriate, and a good image tends to be obtained. The above upper and lower limits can be arbitrarily combined. For example, the content may be 10% by mass or more but less than 45% by mass, 15 to 40% by mass, or 20 to 35% by mass.

[0196] <(E) Photopolymerizable Compound> The photosensitive resin composition of the present invention may contain (E) a photopolymerizable compound from the viewpoint of sensitivity, etc. Examples of the (E) photopolymerizable compound include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as "ethylenic monomers"). Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, and esters of carboxylic acids having one ethylenically unsaturated bond with polyhydric or monohydric alcohols.

[0197] As the (E) photopolymerizable compound, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups per molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably three or more, more preferably four or more, even more preferably five or more, particularly preferably six or more, and preferably ten or less, more preferably eight or less. By setting the number at or above the lower limit, the photosensitive resin composition tends to have high sensitivity, while by setting the number at or below the upper limit, cure shrinkage during polymerization tends to be small. The above upper and lower limits can be arbitrarily combined. For example, the number may be 2 to 10, 3 to 10, 4 to 10, 5 to 8, or 6 to 8. Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyvalent hydroxy compounds, such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, with unsaturated carboxylic acids and polybasic carboxylic acids.

[0198] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate; and similarly, itaconic acid esters in which itaconate is replaced with itaconate, crotonate esters in which cronate is replaced with cronate, or maleate esters in which maleate is replaced with cronate.

[0199] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, etc. Esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single compounds, but include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0200] Other useful polyfunctional ethylenic monomers for use in the present invention include, for example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. These may be used alone or in combination of two or more.

[0201] The content of the (E) photopolymerizable compound in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 18% by mass or less, more preferably 16% by mass or less, even more preferably 13% by mass or less, particularly preferably 10% by mass or less, and preferably 3% by mass or more, more preferably 4% by mass or more, based on the total solids content of the photosensitive resin composition. When the content of the (E) photopolymerizable compound is equal to or less than the above upper limit, the permeability of the developer into the exposed area becomes appropriate, and a good image tends to be obtained. When the content is equal to or greater than the above lower limit, photocuring by ultraviolet irradiation tends to be improved and alkaline developability tends to be good. The above upper and lower limits can be arbitrarily combined. For example, the content may be 3 to 18% by mass, 3 to 16% by mass, 4 to 13% by mass, or 4 to 10% by mass.

[0202] <(F) Photopolymerization Initiator> The photosensitive resin composition of the present invention contains (F) a photopolymerization initiator. (F) The photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and has the function of generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added thereto.

[0203] Examples of the photopolymerization initiator (F) include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives described in JP-A-10-39503; and oxime ester derivatives described in JP-A-2000-80068 and JP-A-2006-36750.

[0204] Examples of titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl].

[0205] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0206] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0207] Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0208] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0209] As the (F) photopolymerization initiator, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are preferred in terms of sensitivity. Among oxime derivatives, oxime ester compounds are preferred in terms of adhesion to the substrate. Using an alkali-soluble resin containing a phenolic hydroxyl group may be disadvantageous in terms of sensitivity. Oxime ester compound photopolymerization initiators have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals. Therefore, they are highly sensitive even in small amounts and stable against thermal reactions, making it possible to design highly sensitive photosensitive resin compositions with small amounts. In particular, from the perspective of light absorption for the i-line (365 nm) of the exposure light source, oxime ester compounds containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) are more preferred because this structural characteristic is well expressed. Currently, the market demands thin black matrices with high light blocking properties, and pigment concentrations are increasing. Under these circumstances, they are particularly effective.

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

[0211]

[0212] In the above formula (22), R ２２ represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, each of which may be substituted.

[0213]

[0214] In formula (23), R ２１ａ represents hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted. R ２１ｂ represents any substituent containing an aromatic ring or heteroaromatic ring.

[0215] In addition, R ２１ａ is R ２１ｂ and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) ｒ -), polyethynylene group (-(C≡C) ｒ -) or a group formed by combining these (where r is an integer of 0 to 3). ２２ａ is R in equation (22). ２２ R in formula (22) represents a group similar to ２２ and R in the above general formula (23) ２２ａ As the alkanoyl group, preferred examples include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms.

[0216] R in formula (23) ２１ａPreferred examples of R include unsubstituted linear alkyl groups or cycloalkylalkyl groups such as unsubstituted methyl, ethyl, and propyl groups, and propyl groups substituted with an N-acetyl-N-acetoxyamino group. ２１ｂ Preferred examples of the group include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenyl sulfide group.

[0217] The photopolymerization initiator of the oxime ester compound is a compound represented by the formula (23): ２１ｂ For the reasons mentioned above, an optionally substituted carbazolyl group is more preferred. Furthermore, a carbazole group having at least one group selected from the group consisting of an optionally substituted aryl group having 6 to 25 carbon atoms, an optionally substituted arylcarbonyl group having 7 to 25 carbon atoms, an optionally substituted heteroaryl group having 5 to 25 carbon atoms, an optionally substituted heteroarylcarbonyl group having 6 to 25 carbon atoms, and a nitro group is preferred. In particular, a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferred. Furthermore, it is desirable for these groups to be bonded to the 3-position of the carbazolyl group.

[0218] Commercially available photopolymerization initiators of such oxime ester compounds include, for example, OXE-02 manufactured by BASF, and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics Co., Ltd.

[0219] Specific examples of the photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but are not limited to these compounds.

[0220]

[0221]

[0222]

[0223] Examples of the ketoxime ester compound include compounds containing a structural moiety represented by the following general formula (24), and preferably, the ketoxime ester compound represented by the following general formula (25).

[0224]

[0225] In formula (24), R ２４ is R in the general formula (22). ２２ is synonymous with.

[0226]

[0227] In formula (25), R ２３ａ represents a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted.

[0228] R ２３ｂ represents any substituent containing an aromatic ring or a heteroaromatic ring. ２３ａ is R ２３ｂ and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) ｒ -), polyethynylene group (-(C≡C) ｒ -) or a group formed by combining these (where r is an integer of 0 to 3).

[0229] R ２４ａrepresents an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, each of which may be substituted. ２４ and R in formula (25) ２４ａ Preferred examples of the alkanoyl group include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.

[0230] R in formula (25) ２３ａ As R , preferred examples include an unsubstituted ethyl group, a propyl group, and a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group. ２３ｂ Preferred examples of the ketoxime ester compound include an optionally substituted carbazoyl group and an optionally substituted phenyl sulfide group. Specific examples of the ketoxime ester compound suitable for the present invention include the compounds exemplified below, but the present invention is not limited to these compounds.

[0231]

[0232]

[0233]

[0234] Commercially available photopolymerization initiators of such ketoxime ester compounds include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Strong Electronics Co., Ltd.

[0235] These oxime and ketoxime ester compounds are known per se and are described in, for example, JP-A Nos. 2000-80068 and 2006-36750. The photopolymerization initiator may be used alone or in combination of two or more.

[0236] Other examples include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropyl phenyl)propanone, and the like. acetophenone derivatives such as 1-(4-phenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl) ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; 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-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone. Among these photopolymerization initiators, oxime ester derivatives are particularly preferred for the reasons mentioned above.

[0237] The content of the (F) photopolymerization initiator is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and particularly preferably 5% by mass or more, based on the total solids content of the photosensitive resin composition. It is also preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 6% by mass or less. When the content of the (F) photopolymerization initiator is equal to or greater than the lower limit, sensitivity tends to improve. When the content is equal to or less than the upper limit, the solubility of the unexposed portion in the developer tends to improve. The upper and lower limits can be arbitrarily combined. For example, it may be 2 to 15% by mass, 3 to 10% by mass, 4 to 7% by mass, or 5 to 6% by mass.

[0238] <Organic Solvent> As the organic solvent, an organic solvent having a boiling point of 100 to 300°C is preferred, and an organic solvent having a boiling point of 120 to 280°C is more preferred. Here, the boiling point is the value at a pressure of 1013.25 hPa. The same applies to all boiling points hereinafter. Examples of organic solvents having a boiling point of 100 to 300°C include the following:

[0239] glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0240] glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0241] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0242] aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; and nitriles such as acetonitrile and benzonitrile.

[0243] Examples of commercially available organic solvents that fall under the above category include mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark; the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names). These organic solvents may be used alone or in combination of two or more.

[0244] When the photosensitive resin composition of the present invention is used to form pixels or a black matrix of a color filter by photolithography, the organic solvent preferably has a boiling point of 100 to 250°C, more preferably 120 to 230°C.

[0245] As the organic solvent, glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, and the like, and have a relatively high solubility of the components in the photosensitive resin composition. Glycol alkyl ether acetates may be used alone or in combination of two or more. Glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. As the other organic solvent, glycol monoalkyl ethers are preferred. Among these, propylene glycol monomethyl ether is preferred in terms of the solubility of the components in the photosensitive resin composition. Glycol monoalkyl ethers have high polarity, and if added in excessive amounts, the (A) pigment tends to aggregate, increasing the viscosity of the resulting photosensitive resin composition and otherwise reducing storage stability. Therefore, when the organic solvent contains glycol monoalkyl ethers, the content of the glycol monoalkyl ethers is preferably 5 to 30 mass% and more preferably 5 to 20 mass% relative to the total mass of the organic solvent.

[0246] Glycol alkyl ether acetates may be used in combination with organic solvents having a boiling point of 200°C or higher (hereinafter sometimes referred to as "high-boiling solvents"). The use of such high-boiling solvents makes the photosensitive resin composition less likely to dry, but also prevents the uniform dispersion of the pigment (A) in the composition from being destroyed by rapid drying. That is, it is effective in preventing the occurrence of foreign matter defects due to precipitation and solidification of the pigment, for example, at the tip of a slit nozzle. The upper limit of the boiling point of the high-boiling solvent is not particularly limited, but is, for example, 300°C or lower. Among high-boiling solvents, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate are preferred due to their high effectiveness. These high boiling point solvents may be used alone or in combination of two or more.

[0247] The content of the high-boiling point solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass, relative to the total mass of the organic solvent. When the content of the high-boiling point solvent is equal to or less than the upper limit, the drying temperature of the composition is slowed, and problems such as poor tact time in the reduced-pressure drying process and pin marks in pre-baking tend to be suppressed in the color filter manufacturing process. When the content of the high-boiling point solvent is 0.5% by mass or more, it tends to be suppressed, for example, from precipitating and solidifying pigments at the tip of a slit nozzle, causing foreign matter defects.

[0248] In the photosensitive resin composition of the present invention, the content of the organic solvent can be appropriately selected taking into account the content of the total solids in the photosensitive resin composition. The content of the total solids relative to the total mass of the photosensitive resin composition of the present invention is 15% by mass or less, preferably 14% by mass or less, more preferably 13% by mass or less, and also preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more. When the content of the total solids in the photosensitive resin composition is equal to or less than the upper limit, the effect of suppressing unevenness in shading due to differences in film thickness is excellent. When the content of the total solids in the photosensitive resin composition is equal to or greater than the lower limit, the viscosity of the photosensitive resin composition increases, improving the dispersion stability of the carbon black (a1), and tending to reduce the average sedimentation velocity at 10% transmittance. The above upper and lower limits can be arbitrarily combined. For example, it may be 10 to 15% by mass, 11 to 14% by mass, or 12 to 13% by mass.

[0249] <Other Components in Photosensitive Resin Composition> In addition to the components described above, the photosensitive resin composition of the present invention may appropriately contain other coloring materials than the pigment (A), thiols, adhesion improvers, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, and the like.

[0250] (Other Coloring Materials) (A) Examples of coloring materials other than pigments include dyes, such as azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0251] Examples of azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Examples of suitable pigments include C.I. Mordant Red 7, C.I. Mordant Yellow 5, and C.I. Mordant Black 7.

[0252] Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60. Other examples of phthalocyanine dyes include C.I. Pad Blue 5, quinoneimine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9, quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64, and nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42 is an example.

[0253] The content of the other coloring materials is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total solid content of the photosensitive resin composition of the present invention.

[0254] (Thiols) The photosensitive resin composition of the present invention may contain thiols in order to increase sensitivity and improve adhesion to a substrate. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane; (trade name: Karenz MT BD1, manufactured by Showa Denko K.K.), butanediol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate); (trade name: Karenz MT PE1, manufactured by Showa Denko K.K.), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko K.K. These may be used alone or in combination of two or more.As the thiols, polyfunctional thiol compounds such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are preferred, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferred, and Karenz MT PE1 is particularly preferred.

[0255] When the photosensitive resin composition of the present invention contains thiols, the content of the thiols 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, and is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition. If the content of the thiols is equal to or greater than the lower limit, there is a tendency for sensitivity reduction to be suppressed, and if it is equal to or less than the upper limit, there is a tendency for storage stability to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.1 to 10% by mass, 0.3 to 10% by mass, or 0.5 to 5% by mass.

[0256] (Adhesion Improver) The photosensitive resin composition of the present invention may contain an adhesion improver to improve adhesion to the substrate. Examples of adhesion improvers include silane coupling agents and titanium coupling agents, with silane coupling agents being particularly preferred. Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shin-Etsu Silicones Co., Ltd.), and Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., Ltd.). One type of silane coupling agent may be used alone, or two or more types may be used in combination.

[0257] The photosensitive resin composition of the present invention may contain an adhesion improver other than a silane coupling agent and a titanium coupling agent. Examples of adhesion improvers other than a silane coupling agent and a titanium coupling agent include phosphoric acid-based adhesion improvers and other adhesion improvers. As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferred, and among them, those represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0258]

[0259] In formulas (g1), (g2), and (g3), R ５１ each independently represents a hydrogen atom or a methyl group, l and l' each independently represents an integer of 1 to 10, and m each independently represents 1, 2, or 3. An example of other adhesion improvers is TEGO*Add Bond LTH (manufactured by Evonik). These phosphate group-containing compounds and other adhesion agents may be used alone or in combination of two or more.

[0260] When the photosensitive resin composition of the present invention contains an adhesion improver, the content of the adhesion improver in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, based on the total solids content of the photosensitive resin composition. If the content of the adhesion improver is equal to or greater than the lower limit, adhesion tends to be improved, while if it is equal to or less than the upper limit, developability tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the content may be 0.01 to 5% by mass, 0.01 to 3% by mass, 0.1 to 2% by mass, or 0.5 to 1.5% by mass.

[0261] (Coatability Improver) The photosensitive resin composition of the present invention may contain a coatability improver to improve coatability. Examples of the coatability improver include surfactants. Examples of surfactants that can be used include anionic, cationic, nonionic, and amphoteric surfactants. Among these, nonionic surfactants are preferred because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are particularly effective in terms of coatability.

[0262] Examples of surfactants that can be used as coatability improvers include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos Corporation), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicones Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unicar Co., Ltd.) and FC4430 (manufactured by 3M Japan Co., Ltd.). One type of coatability improver may be used alone, or two or more types may be used in combination.

[0263] When the photosensitive resin composition of the present invention contains a coatability improver, the content of the coatability improver in the photosensitive resin composition is not particularly limited, but 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, based on the total solids content of the photosensitive resin composition. If the content of the coatability improver is equal to or greater than the lower limit, coating uniformity tends to be improved, while if it is equal to or less than the upper limit, resist sensitivity tends not to decrease. The above upper and lower limits can be arbitrarily combined. For example, the content may be 0.01 to 1.0% by mass, 0.01 to 0.7% by mass, 0.05 to 0.5% by mass, or 0.05 to 0.3% by mass.

[0264] <Physical Properties of Photosensitive Resin Composition> The photosensitive resin composition of the present invention has an average sedimentation velocity at 10% transmittance measured by centrifugal sedimentation of 800 μm / h or less. The average sedimentation velocity at 10% transmittance is measured using a centrifugal sedimentation evaluation device (e.g., LUMiSizer (registered trademark) from LUM Corporation). Centrifugal force is applied to a sample placed in a measurement cell to promote particle sedimentation, and parallel light is irradiated onto the cell. Information on the transmittance of light transmitted through the cell and the position of particles within the cell (transmitted light profile) is acquired in real time using multiple CCD line sensors arranged along the direction of centrifugal force application (particle movement direction). Detailed measurement conditions are as described in the Examples below. The transmitted light profile is usually expressed as a graph with particle position on the horizontal axis and transmittance on the vertical axis. When centrifugal force is applied, particles are classified according to particle diameter. At the end of the measurement, particles tend to have larger particle diameters and lower transmittance toward the tip of the cell in the direction of centrifugal force application. Then, from the obtained transmitted light profile, for each particle present at the 10% transmittance position at the end of the measurement, the sedimentation velocity (μm / h) is calculated by dividing the travel distance (μm) by the measurement time (hours), and these values ​​are averaged to determine the average sedimentation velocity at 10% transmittance. According to the inventor's studies, the behavior of particles at 10% transmittance is useful as an indicator of the likelihood of generation of foreign matter derived from carbon black (a1). When the total solids content is 15% by mass or less and the carbon black (a1) content relative to the total solids content exceeds 40% by mass, foreign matter derived from carbon black (a1) tends to be generated easily. However, by setting the average sedimentation velocity at 10% transmittance to 800 μm / h or less, the generation of foreign matter derived from carbon black (a1) can be suppressed. The average sedimentation velocity at 10% transmittance is preferably 700 μm / h or less, more preferably 650 μm / h or less, and even more preferably 600 μm / h or less. The lower the average sedimentation velocity at 10% transmittance, the better, and the lower limit is not particularly limited, but is, for example, 0.1 μm / h. For example, it may be 0.1 to 800 μm / h, 0.1 to 700 μm / h, 0.1 to 650 μm / h, or 0.1 to 600 μm / h.

[0265] The average 10% sedimentation velocity at transmittance of the photosensitive resin composition can be adjusted, for example, by adjusting the (B) dispersant, (C) dispersion aid, the ratio of total solids to the total mass of the photosensitive resin composition, the ratio of carbon black (a1) to the total solids, the dispersion treatment conditions during production of the photosensitive resin composition, and by mixing a photosensitive resin composition with a high average 10% sedimentation velocity at transmittance with a photosensitive resin composition with a low average 10% sedimentation velocity at transmittance. As the total solids content increases, the viscosity of the photosensitive resin composition increases, suppressing sedimentation and reducing the average 10% sedimentation velocity at transmittance. Furthermore, as the carbon black (a1) content relative to the total solids decreases, the concentration of carbon black (a1) in the photosensitive resin composition decreases, making it less likely to aggregate, resulting in a smaller average 10% sedimentation velocity at transmittance. Regarding dispersion treatment conditions, for example, the average 10% sedimentation velocity at transmittance of the photosensitive resin composition can be reduced by extending the treatment time of the (A) pigment dispersion treatment. As described above, the average sedimentation velocity at 10% transmittance can also be adjusted by the type of carbon black (a1) used in the photosensitive resin composition, the content ratio of the (B) dispersant, and the content ratio of the (A) pigment to the (B) dispersant.

[0266] The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from this viewpoint, it is preferable that the composition exhibits a black color. Furthermore, the optical density (OD) per μm of film thickness of the coating film is preferably 3.8 or more, more preferably 4.0 or more, and even more preferably 4.2 or more. When the OD per μm of film thickness is equal to or greater than the lower limit, the light-shielding properties are excellent. The upper limit of the OD per μm of film thickness is not particularly limited, but is, for example, 6.0. The OD per μm of film thickness may be, for example, 3.8 to 6.0, 4.0 to 6.0, or 4.2 to 6.0.

[0267] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present invention can be produced, for example, by preparing a pigment dispersion containing (A) a pigment and an organic solvent, and then mixing this pigment dispersion with (D) an alkali-soluble resin and (F) a photopolymerization initiator, and, if necessary, an additional organic solvent and optional components. The pigment dispersion and its preparation method will be described in detail later. The temperature during mixing of the components is, for example, 20 to 30°C. After mixing, the obtained photosensitive resin composition may be subjected to a dispersion treatment or a filtration treatment using a filter, etc., if necessary.

[0268] [Pigment Dispersion] The pigment dispersion contains (A) a pigment and an organic solvent. The pigment dispersion may contain (B) a dispersant. The pigment dispersion may contain (C) a dispersing aid. The pigment dispersion may further contain other components in addition to (A) the pigment, (B) the dispersing agent, (C) the dispersing aid, and the organic solvent, as necessary. Examples of other components include other components blended in the photosensitive resin composition of the present invention.

[0269] The content of the (A) pigment relative to the total solid content in the pigment dispersion is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. If the content of the (A) pigment is equal to or greater than the above-mentioned lower limit, the light-blocking properties of the resulting cured product tend to be better, while if it is equal to or less than the above-mentioned upper limit, the dispersibility tends to be better. The above upper and lower limits can be combined arbitrarily. For example, it may be 50 to 99% by mass, 60 to 95% by mass, or 70 to 90% by mass.

[0270] When the pigment dispersion contains a (B) dispersant, the content ratio, on a mass basis, of the (A) pigment to the (B) dispersant in the pigment dispersion ((A) pigment / (B) dispersant) is the same as the content ratio, on a mass basis, of the (A) pigment to the (B) dispersant in the photosensitive resin composition of the present invention.

[0271] When the pigment dispersion contains a (C) dispersing aid, the content of the (C) dispersing aid relative to the total solids content of the pigment dispersion 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, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. When the content of the (C) dispersing aid is equal to or greater than the lower limit, dispersion stability tends to be better, while when it is equal to or less than the upper limit, developability tends to be stable and substrate adhesion tends to be better. The upper and lower limits can be arbitrarily combined. For example, the content may be 0.1 to 10% by mass, 0.5 to 5% by mass, or 1.0 to 3% by mass.

[0272] The content of other components relative to the total solid content of the pigment dispersion is preferably 5% by mass or less, more preferably 1% by mass or less, and may be 0% by mass.

[0273] The content of the organic solvent in the pigment dispersion can be appropriately selected in consideration of the content of the total solid content in the pigment dispersion.

[0274] The content of all solids in the pigment dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total mass of the pigment dispersion, from the viewpoint of light-blocking properties. Also, from the viewpoint of viscosity stability, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content may be 10 to 60% by mass, 20 to 50% by mass, or 30 to 40% by mass.

[0275] [Preparation of Pigment Dispersion] The pigment dispersion can be produced, for example, by mixing (A) a pigment and an organic solvent, and, if necessary, optional components such as (B) a dispersant and (C) a dispersing aid, and then subjecting the resulting mixture to a dispersion treatment.

[0276] The dispersion treatment reduces the particle size of the (A) pigment, thereby reducing the average sedimentation velocity at 10% transmittance of the photosensitive resin composition. It also improves the coating properties and light-blocking ability of the photosensitive resin composition. In particular, the use of a polymer dispersant as the (B) dispersant inhibits thickening over time of the resulting pigment dispersion and the photosensitive resin composition containing it (leading to excellent dispersion stability).

[0277] Dispersion treatment can be carried out using known dispersion treatment devices such as paint conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills, and homogenizers. When dispersion treatment is performed using a sand grinder, glass beads or zirconia beads with a diameter of approximately 0.1 to 8 mm are preferably used. Dispersion treatment conditions are not particularly limited, but the temperature ranges from 0°C to 100°C, for example, and preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, so it should be adjusted appropriately. A guideline for dispersion is to control the dispersion state of the (A) pigment so that the 20° specular gloss (JIS Z8741) of the coating film of the photosensitive resin composition is in the range of 100 to 200. When the gloss of the coating film of the photosensitive resin composition is low, the dispersion treatment is often insufficient, leaving coarse pigment particles, which may result in insufficient developability, adhesion, resolution, and other properties. Furthermore, if the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment will be crushed to produce a large number of ultrafine particles, which tends to impair dispersion stability. After the dispersion treatment, if necessary, the obtained dispersion can be filtered using a filter or the like to separate the beads used in the dispersion treatment from the pigment dispersion, for example.

[0278] The photosensitive resin composition of the present invention can be used as a resist for components constituting a color filter, such as pixels and black matrices. When the photosensitive resin composition of the present invention is for a black matrix, it contains a black colorant such as a black pigment. The photosensitive resin composition of the present invention can also be used as a resist for colored spacers. The photosensitive resin composition of the present invention can also be used to form partition walls, particularly partition walls for separating the organic layer of an organic electroluminescent device. Examples of organic layers in organic electroluminescent devices include organic layers used as hole injection layers, hole transport layers, or hole transport layers on hole injection layers, as described in JP 2016-165396 A.

[0279] [Cured Product] The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. The cured product of the present invention can be suitably used as a component constituting a color filter, such as a pixel or a black matrix. The cured product of the present invention can also be used as a colored spacer. The cured product of the present invention can also be used as a partition wall, particularly a partition wall for partitioning the organic layer of an organic electroluminescent device.

[0280] [Black Matrix] A black matrix made of the cured product of the present invention will be described according to its manufacturing method. The black matrix made of the cured product of the present invention can be formed, for example, by applying the photosensitive resin composition of the present invention to a support on which the black matrix is ​​to be provided, drying the composition, placing a photomask on the dried coating film, exposing the composition through the photomask (imagewise exposure), developing the composition, and optionally curing the composition.

[0281] (1) Support The material of the support for forming the black matrix is ​​not particularly limited as long as it has adequate strength, but a transparent substrate is mainly used. Examples of materials for the transparent substrate include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass. Among these, glass and heat-resistant resins are preferred from the viewpoint of heat resistance. A transparent electrode such as ITO or IZO may also be formed on the surface of the transparent substrate. The black matrix can also be formed on a support other than a transparent substrate, such as a TFT array. To improve surface properties such as adhesion, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, or thin film formation treatment using various resins such as silane coupling agents or urethane resins, as necessary. The thickness of the transparent substrate is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. When a thin film of various resins is formed, the thickness of the film is preferably in the range of 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0282] (2) Formation of Black Matrix (2-1) Coating of Photosensitive Resin Composition Coating of the photosensitive resin composition for the black matrix onto a support can be carried out by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among these, the die coating method is preferred from an overall viewpoint, since it significantly reduces the amount of coating liquid used, is completely free from the influence of mist and the like that adheres when using spin coating, and suppresses the generation of foreign matter.

[0283] The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. By setting the thickness to the upper limit or less, pattern development tends to be easy, and gap adjustment in the liquid crystal cell fabrication process also tends to be easy. By setting the thickness to the lower limit or more, desired color expression tends to be easy.

[0284] (2-2) Drying of Coating Film After applying the photosensitive resin composition to the support, the coating film is preferably dried using a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected depending on the type of liquid medium (organic solvent, water) contained in the photosensitive resin composition, the performance of the dryer used, and other factors. For example, drying conditions are selected from a temperature range of 40 to 200°C and a time range of 15 seconds to 5 minutes, preferably a temperature range of 50 to 130°C and a time range of 30 seconds to 3 minutes. The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and resulting in poor development. This coating film drying process may also be performed using a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without increasing the temperature.

[0285] (2-3) Exposure Image exposure is carried out by placing a photomask on a coating film of the photosensitive resin composition and irradiating the coating film with light having a wavelength ranging from the ultraviolet region to the visible region through the photomask. A negative mask pattern is typically used as the photomask. If necessary, an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the coating film before exposure in order to prevent a decrease in the sensitivity of the coating film due to oxygen. The light source used for image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. When using light of a specific wavelength, an optical filter can also be used.

[0286] (2-4) Development Development is carried out using an organic solvent or an aqueous solution containing an alkaline compound and a surfactant. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0287] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used alone or in combination.

[0288] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkylbetaines and amino acids.

[0289] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

[0290] There are no particular restrictions on the conditions for the development treatment. The development temperature is preferably 10 to 50° C., more preferably 15 to 45° C., and even more preferably 20 to 40° C. The development method can be any of immersion development, spray development, brush development, ultrasonic development, etc.

[0291] (2-5) Curing Treatment Examples of the curing treatment include heat curing treatment and photocuring treatment, with heat curing treatment being preferred. The heat curing treatment conditions are a temperature selected from the range of 100 to 280°C, preferably 150 to 250°C, and a time selected from the range of 5 to 60 minutes.

[0292] The height of the black matrix thus formed is preferably 0.5 to 5 μm, more preferably 0.8 to 4 μm, and the optical density (OD) per μm of thickness is preferably 3.8 or more, more preferably 4.0 or more, and even more preferably 4.2 or more.

[0293] [Color Filter] A photosensitive resin composition containing a colorant of one of red (R), green (G), and blue (B) colors is applied to a transparent substrate provided with a black matrix using the same processes as those described above in (2-1) to (2-5). After drying, a photomask is placed on the coating film, and a pixel image is formed by imagewise exposure through the photomask, development, and, if necessary, heat curing or photocuring to form a colored layer. This operation is performed for each of the photosensitive resin compositions of the three colors R, G, and B, thereby forming a color filter. The order of these processes is not limited to the above.

[0294] (2-6) Formation of Transparent Electrode The color filter can be used as a part of a color display, liquid crystal display device, etc. by forming a transparent electrode such as ITO on the image in its current state. In order to improve surface smoothness and durability, a topcoat layer of polyamide, polyimide, etc. can be formed on the image as needed. In some applications, such as those using a planar alignment driving system (IPS mode), a transparent electrode may not be formed.

[0295] [Colored Spacer] When a spacer is used in a TFT-type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and colored spacers are used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 describes making the spacer light-blocking. Colored spacers made from the cured product of the present invention can be formed in the same manner as the above-mentioned black matrix, except that a mask for colored spacers is used.

[0296] [Partition Wall] The partition wall made of the cured product of the present invention will be described according to its production method. The partition wall made of the cured product of the present invention can be formed, for example, by a method in which the photosensitive resin composition of the present invention is applied to a support on which the partition wall is to be provided, dried, a photomask is placed on the dried coating film, exposure (imagewise exposure) is performed through the photomask, development is performed, and a curing treatment is performed as necessary.

[0297] (3-1) Support As a support for forming the partition walls, the same support as that for forming the black matrix described above can be used.

[0298] (3-2) Formation of Partition Walls In the method for forming partition walls, specific methods for applying the photosensitive resin composition to the support, drying, exposing, developing and curing can be the same as those used in the formation of the black matrix described above.

[0299] The size and shape of the partition wall are adjusted as appropriate depending on the specifications of the organic electroluminescent device to which it is applied, but the height of the partition wall formed from the photosensitive resin composition is preferably about 0.5 to 10 μm.

[0300] [Organic Electroluminescent Device] Various organic electroluminescent devices are manufactured using a support provided with partition walls manufactured by the above-described method. For example, although the method for forming an organic electroluminescent device is not particularly limited, the organic electroluminescent device is preferably manufactured by forming partition walls on a support by the above-described method and then forming organic layers such as pixels. Examples of methods for forming the organic layer include a vapor deposition method in which a functional material is sublimated in a vacuum and deposited in an area surrounded by partition walls on a substrate to form a film, and wet processes such as a casting method, a spin coating method, and an inkjet printing method.

[0301] Examples of organic electroluminescent device types include bottom-emission and top-emission types. Bottom-emission devices are fabricated, for example, by forming a partition wall on a glass substrate on which a transparent electrode is laminated, and then laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the partition wall. On the other hand, top-emission devices are fabricated, for example, by forming a partition wall on a glass substrate on which a metal electrode layer is laminated, and then laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition wall. Examples of light-emitting layers include organic electroluminescent layers such as those described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0302] The layer structure is not limited to this, and for example, each of the hole transport layer and the electron transport layer may have a laminate structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0303] The organic electroluminescent element may be formed with each RGB color separated for each opening, or two or more colors may be stacked in one opening. The organic electroluminescent element may have a sealing layer from the viewpoint of improving reliability. The sealing layer has the function of preventing moisture in the air from being adsorbed to the organic electroluminescent element and reducing the luminous efficiency. The organic electroluminescent element may have a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By disposing the low-reflection film at the interface between air and the element, the refractive index gap can be reduced, and it is expected that reflection at the interface can be suppressed. For example, moth-eye structure and super multilayer film technology can be applied to such a low-reflection film.

[0304] When organic electroluminescent elements are used as pixels of an image display device, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent element in order to prevent light from the light-emitting layer of one pixel from leaking to other pixels and, further, to prevent degradation of image quality due to reflection of external light when the electrodes, etc., are made of metal. In organic electroluminescent elements, electrodes are provided on the upper and lower surfaces of the partition walls, so from the viewpoint of insulation, it is preferable that the partition walls have high resistance and low dielectric constant. Therefore, when a colorant is used to impart light-shielding properties to the partition walls, it is preferable to use the above-mentioned organic pigment having high resistance and low dielectric constant.

[0305] [Image display device] The image display device of the present invention comprises the cured product of the present invention. Examples of the image display device of the present invention include image display devices comprising the black matrix or partition walls described above. The image display device is not particularly limited as long as it is a device that displays images or videos, and examples thereof include liquid crystal display devices and organic EL displays described below.

[0306] [Liquid Crystal Display Device] The liquid crystal display device of the present invention can be produced, for example, by using a color filter having the above-described black matrix. The order and position of forming the color pixels and the black matrix are not particularly limited.

[0307] Liquid crystal display devices are typically manufactured by forming an alignment film on a color filter, dispersing spacers on the alignment film, and then bonding it to an opposing substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell, and the cell is connected to the opposing electrode. A resin film such as polyimide is suitable for the alignment film. Gravure printing and / or flexographic printing are typically used to form the alignment film, with a thickness of several tens of nanometers. After the alignment film is cured by thermal baking, it is surface-treated by ultraviolet irradiation or treatment with a rubbing cloth to create a surface condition that allows the tilt of the liquid crystal to be adjusted.

[0308] The size of the spacer used depends on the gap (gap) with the opposing substrate, and a size of 2 to 8 μm is preferable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. An array substrate is usually used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly preferable.

[0309] The gap between the opposing substrate and the substrate is preferably in the range of 2 to 8 μm, although it varies depending on the application of the liquid crystal display device. After bonding to the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell with the sealed periphery is cut into panel units, and then the pressure is reduced in a vacuum chamber. The liquid crystal injection port is immersed in liquid crystal, and the liquid crystal is then injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction in the liquid crystal cell is 1×10 －７ ~1 x 10 －２ Pa is preferred, 1×10 －６ ~1 x 10 －３ Pa is more preferable. It is also preferable to heat the liquid crystal cell during decompression, and the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. The heating is preferably maintained during decompression for 10 to 60 minutes. The liquid crystal cell is then immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed at the liquid crystal injection port by curing a UV curable resin, thereby completing a liquid crystal display device (panel).

[0310] The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, for example, a lyotropic liquid crystal, or a thermotropic liquid crystal. Known thermotropic liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0311] [Organic EL Display] The organic EL display of the present invention can be produced using, for example, a color filter having the above-described black matrix or an organic electroluminescent element having the above-described partition wall.

[0312] When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1 , a color filter having a pattern (i.e., pixels 20 and a black matrix (not shown) provided between adjacent pixels 20) formed from a photosensitive resin composition is first produced on a transparent support substrate 10, and an organic light-emitting element 500 is then laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40, thereby producing an organic EL element 100. Note that at least one of the pixels 20 and the black matrix is ​​produced using the photosensitive resin composition of the present invention. Examples of methods for laminating the organic light-emitting element 500 include a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the top surface of the color filter, and a method of laminating the organic light-emitting element 500 formed on a separate substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, an organic EL display can be produced by, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, by Shizuo Tokito, Chinaya Adachi, and Hideyuki Murata).

[0313] The color filter of the present invention can be applied to both passively driven organic EL displays and actively driven organic EL displays.

[0314] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0315] <Preparation of Pigment Dispersion Liquid-1> Pigment dispersion liquid-1 was prepared by the following procedure. First, a mixed liquid was obtained by mixing the following pigment-1, dispersant-1, dispersing aid-1, and solvent. Pigment-1: "NEROX 555" (carbon black) manufactured by Orion Engineered Carbons; 100 parts by mass. Dispersant-1: "DISPERBYK-167" (urethane-based polymer dispersant having a basic functional group) manufactured by BYK-Chemie; 18.2 parts by mass (solid content equivalent). Dispersing aid-1: "S12000-S" (pigment derivative, sulfonic acid derivative of phthalocyanine) manufactured by The Lubrizol Corporation; 2 parts by mass. Solvent: propylene glycol monomethyl ether acetate; 223.2 parts by mass.

[0316] Next, 180 g of beads were added to 60 g of the obtained mixed liquid, and a dispersion treatment was carried out for 6 hours at a temperature range of 25 to 45°C using a paint shaker. Zirconia beads with a diameter of 0.5 mm were used. After dispersion was completed, the beads and the dispersion were separated using a filter to obtain Pigment Dispersion Liquid-1 with a solid content of 35% by mass.

[0317] <Preparation of Pigment Dispersion Liquid-2> Pigment Dispersion Liquid-2 was prepared in the same manner as in the preparation of Pigment Dispersion Liquid-1, except that a mixed liquid was obtained by mixing the following Pigment-2, Dispersant-1, Dispersing Aid-1, and solvent. Pigment-2: "RAVEN 1060" (carbon black) manufactured by BIRLA CARBON; 100 parts by mass. Dispersant-1: "DISPERBYK-167" (urethane-based polymer dispersant having a basic functional group) manufactured by BYK-Chemie; 20 parts by mass (solids content equivalent). Dispersing Aid-1: "S12000-S" (pigment derivative, sulfonic acid derivative of phthalocyanine) manufactured by The Lubrizol Corporation; 2 parts by mass. Solvent: propylene glycol monomethyl ether acetate; 232.8 parts by mass.

[0318] <Preparation of Pigment Dispersion Liquid-3> Pigment Dispersion Liquid-3 was obtained in the same manner as in the preparation of Pigment Dispersion Liquid-2, except that Pigment-3 below was used instead of Pigment-2. Pigment-3: NEROX 305 (carbon black) manufactured by Evonik Degussa; 100 parts by mass.

[0319] <Preparation of Pigment Dispersion Liquid-4> Pigment Dispersion Liquid-4 was obtained in the same manner as in the preparation of Pigment Dispersion Liquid-1, except that the dispersion treatment time was changed to 3 hours.

[0320] <Preparation of Pigment Dispersion Liquid-5> Pigment Dispersion Liquid-5 was prepared in the same manner as in the preparation of Pigment Dispersion Liquid-1, except that a mixed liquid was obtained by mixing the following Pigment-2, Dispersant-1, Dispersing Aid-1, and solvent. Pigment-2: "RAVEN 1060" (carbon black) manufactured by BIRLA CARBON; 100 parts by mass. Dispersant-1: "DISPERBYK-167" (urethane-based polymer dispersant having a basic functional group) manufactured by BYK-Chemie; 11.63 parts by mass (solid content equivalent). Dispersing Aid-1: "S12000-S" (pigment derivative, sulfonic acid derivative of phthalocyanine) manufactured by The Lubrizol Corporation; 1.98 parts by mass. Solvent: propylene glycol monomethyl ether acetate; 215.6 parts by mass.

[0321] <Physical Properties of Pigments> The average primary particle size, DBP absorption, and specific surface area measured by the BET method for Pigments-1 to -3 were measured using the following methods. The results are shown in Table 1. [Average Primary Particle Size] The pigments were observed using a TEM, and the minute spherical portions constituting the primary aggregates (aggregates) were considered as single particles (primary particles). The diameters of 10 or more such minute particulate portions were measured as a perfect circle approximation, and the average value was used as the average primary particle size. [DBP Absorption] Dibutyl phthalate (DBP) was gradually added dropwise to the pigment being stirred with a rotor blade, and the DBP absorption was measured from the relationship between the amount of DBP added and the torque applied to the rotor blade. In accordance with JIS K 6217-4, the amount of DBP added at 70% of the maximum torque was calculated. [Specific Surface Area Measured by the BET Method] Nitrogen was adsorbed onto the pigment, and the specific surface area was calculated from the amount of adsorption. BET measurements were carried out in accordance with the standard of JIS K 6217-7.

[0322]

[0323] <Synthesis of alkali-soluble resin-2>

[0324]

[0325] 98.0 parts by mass of the epoxy compound (epoxy equivalent: 245) represented by the structural formula above, 28.8 parts by mass of acrylic acid, 113.0 parts by mass of 3-methoxybutyl acetate, 1.1 parts by mass of triphenylphosphine, and 0.02 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was reacted with stirring at 90°C until the acid value reached 5 mgKOH / g or less, yielding an epoxy acrylate solution. The reaction took 15 hours.

[0326] To 189.1 parts by mass of the epoxy acrylate solution, 11.8 parts by mass of biphenyltetracarboxylic dianhydride (BPDA) and 30.4 parts by mass of tetrahydrophthalic anhydride (THPA) were added, and the mixture was allowed to react while being stirred and slowly heated to 105°C. When the solution became transparent, it was diluted with 3-methoxybutyl acetate to adjust the solids content to 55% by mass, and alkali-soluble resin-2 having an acid value of 110 mgKOH / g and a weight average molecular weight (Mw) of 2,800 was obtained.

[0327] (Examples 1 and 2 and Comparative Examples 1 to 6) <Preparation of Photosensitive Resin Composition> Each component was added so that the ratio of the solid content of each component in the total solid content would be the blending ratio in Table 2, and propylene glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate (MBA), and diethylene glycol monoethyl ether acetate (EDGAC) were further added so that the content ratio of the total solid content of the photosensitive resin composition would be the solid content concentration in Table 2 and further so that the mass ratio of PGMEA / MBA / EDGAC in the solvent would be 75 / 23 / 2, followed by stirring and dissolution to obtain a photosensitive resin composition.

[0328] In Example 2, Pigment Dispersion-1 and Pigment Dispersion-5 were added so that Pigment-1 and Pigment-2 were mixed in the same ratio, thereby obtaining a photosensitive resin composition.

[0329] In Table 2, the materials other than the pigment dispersion and alkali-soluble resin-2 are as follows. Alkali-soluble resin-1: "ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight (Mw) 6500, acid value 98 mgKOH / g, carboxyl group-containing epoxy (meth)acrylate resin). Photopolymerizable compound-1: "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd. (multifunctional acrylate monomer). Photopolymerizable initiator-1: "TR-PBG-304" manufactured by Changzhou Strong Electronic New Materials Co., Ltd. (oxime ester compound having a carbazole skeleton). The structures are as follows:

[0330]

[0331] Adhesion improver-1: "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd. (a reaction product of 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate and phosphoric anhydride). Surfactant-1: "MEGAFAC F559" manufactured by DIC Corporation (a fluorine-based surfactant).

[0332] <Measurement of Average Sedimentation Velocity at 10% Transmittance> The average sedimentation velocity at 10% transmittance for each photosensitive resin composition obtained was measured using a centrifugal sedimentation evaluation device (LUMiSizer 610 manufactured by LUM Corporation). Specifically, 0.3 mL of the photosensitive resin composition was dispensed into a dedicated polyamide cell with an optical path length of 2 mm, and the cell was placed in a rotor (diameter 170 mm). Centrifugal force was applied at 4000 rpm (approximately 2055 G) for 1 hour while irradiating the cell with light (wavelength 865 nm) at a temperature of 15°C. During this time, a transmitted light profile (vertical axis: transmittance, horizontal axis: position information) was obtained every 30 seconds. From the obtained transmitted light profile, the average sedimentation velocity at 10% transmittance was obtained using analysis software. The results are shown in Table 2.

[0333] <Evaluation of Photosensitive Resin Composition> Each of the obtained photosensitive resin compositions was evaluated as follows. The results are shown in Table 2.

[0334] [Measurement of optical density per unit film thickness (OD / FT)] The photosensitive resin composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing would be 1.15 μm, and the applied film was dried under reduced pressure at 100 Pa for 30 seconds, and then dried on a hot plate at 110° C. for 120 seconds. The obtained coating film was subjected to a photolithography process without using a mask, with an intensity of 45 mW / cm at a wavelength of 365 nm. ２ The exposure dose was 50 mJ / cm ２ The entire surface was exposed to light so that the film thickness was 0.04% by mass. Subsequently, shower development was performed at 23°C and a water pressure of 0.05 MPa for 80 seconds using a developer consisting of a 0.04% by mass aqueous solution of potassium hydroxide (KOH). Development was then stopped with pure water and the film was washed with a water spray. The substrate was then post-baked in an oven at 230°C for 30 minutes to obtain a substrate for optical density measurement. The optical density (OD) of the obtained substrate for optical density measurement was measured using a transmission densitometer (361T(V) manufactured by X-Rite), and the film thickness was measured using a scanning white light interference microscope (VS1530 manufactured by Hitachi High-Technologies Corporation). The optical density per unit film thickness (OD / FT) was calculated from the optical density (OD) and film thickness.

[0335] [Foreign matter evaluation] The photosensitive resin composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing would be 1.15 μm, and the substrate was dried under reduced pressure at 100 Pa for 30 seconds, and then dried on a hot plate at 110° C. for 120 seconds. The substrate was then heat cured (post-baked) at 230° C. for 30 minutes in an oven to obtain a substrate for foreign matter evaluation. The surface of the substrate for foreign matter evaluation was observed with an optical microscope, and the number of protruding foreign matters present within a 7 cm × 1 mm area in the center of the substrate for foreign matter evaluation was counted, and the results obtained were evaluated as follows: C: 30 or more. B: 15 or more but less than 30. A: Less than 15.

[0336] [Unevenness Evaluation] The photosensitive resin composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing would be 1.15 μm, and then dried under reduced pressure at 100 Pa for 30 seconds, followed by drying on a hot plate at 110° C. for 120 seconds to obtain a substrate for unevenness evaluation. The color tone of the surface of the substrate for unevenness evaluation was visually observed, and unevenness in shading was evaluated as follows: It is presumed that unevenness in shading is mainly due to differences in the film thickness of the coating film. C: Unevenness in shading is clearly visible over the entire surface, which is problematic in practical use. B: Unevenness in shading is faintly visible in some areas, but is not a problem in practical use. A: There is no unevenness in shading and the surface appears uniform.

[0337]

[0338] As shown in Table 2, the coating film (cured product) of the photosensitive resin composition of Example 1 had a high OD / FT, i.e., excellent light-shielding properties, and the occurrence of foreign matter and unevenness was suppressed. On the other hand, the coating films of the photosensitive resin compositions of Comparative Examples 1, 4, and 5, which had an average sedimentation velocity at 10% transmittance of more than 800 μm / h, contained a large amount of foreign matter. In particular, clear unevenness occurred in Comparative Examples 1 and 5. Furthermore, the coating film of the photosensitive resin composition of Comparative Example 2, in which the carbon black content relative to the total solids content was 40% by mass or less, had a low OD / FT, indicating poor light-shielding properties. Furthermore, the coating film of the photosensitive resin composition of Comparative Example 3, in which the solids concentration was more than 15% by mass, contained a large amount of foreign matter.

[0339] REFERENCE SIGNS LIST 10 transparent support substrate 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 51 hole injection layer 52 hole transport layer 53 light-emitting layer 54 electron injection layer 55 cathode 100 organic EL element 500 organic light-emitting body

Claims

1. A photosensitive resin composition comprising (A) a pigment, (D) an alkali-soluble resin, (F) a photopolymerization initiator, and an organic solvent, the pigment (A) contains carbon black (a1), the content ratio of the total solid content to the total mass of the photosensitive resin composition is 15 mass% or less, the content of the carbon black (a1) relative to the total solid content of the photosensitive resin composition is more than 40 mass%; A photosensitive resin composition having an average sedimentation velocity at 10% transmittance measured by centrifugal sedimentation of 800 μm / h or less.

2. A photosensitive resin composition as described in claim 1, wherein the total solid content relative to the total mass of the photosensitive resin composition is 14 mass% or less.

3. 2. The photosensitive resin composition according to claim 1, wherein the carbon black (a1) has a dibutyl phthalate absorption of 55 mL / 100 g or more and 100 mL / 100 g or less.

4. 2. The photosensitive resin composition according to claim 1, wherein the carbon black (a1) has an average primary particle size of 15 nm or more and 30 nm or less.

5. The specific surface area of ​​the carbon black (a1) measured by the BET method is 115 m ２ The photosensitive resin composition according to claim 1, wherein the solubility is 1 / g or less.

6. The photosensitive resin composition according to claim 1 , further comprising (B) a dispersant.

7. 7. The photosensitive resin composition according to claim 6, wherein a content ratio of the pigment (A) to the dispersant (B) (pigment (A) / dispersant (B)) on a mass basis is 6.5 or less.

8. The photosensitive resin composition according to claim 1 , further comprising (E) a photopolymerizable compound.

9. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (D) is an epoxy (meth)acrylate resin.

10. A photosensitive resin composition as described in claim 1, wherein the content ratio of carbon black (a1) to the total solid content of the photosensitive resin composition is 52 mass% or more.

11. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.

12. A black matrix comprising the cured product according to claim 11.

13. An image display device comprising the cured product according to claim 11.