Pigment dispersions, photosensitive resin compositions, cured materials, black matrices, and image display devices

Abstract

This invention provides a pigment dispersion that yields a photosensitive resin composition with excellent solubility and fine-line adhesion, and a photosensitive resin composition using the same. The pigment dispersion of this invention contains (A) a pigment, (B) a dispersant, and (C) a sulfonic acid-containing compound, wherein the conductivity of the sulfonic acid-containing compound (C) is 2000 μS / cm or more and 9000 μS / cm or less, and the acid value of the sulfonic acid-containing compound (C) is 40 mgKOH / g or more.

Description

[Technical Field]

[0001] This invention relates to a pigment dispersion, a photosensitive resin composition, a cured material, a black matrix (hereinafter sometimes abbreviated as "BM"), and an image display device. This application claims priority based on Japanese Patent Application No. 2021-171566 filed on October 20, 2021, and Japanese Patent Application No. 2021-199773 filed on December 9, 2021, the contents of which are incorporated herein by reference. [Previous Technology]

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

[0003] As a representative manufacturing method for color filters, the pigment dispersion method is known. In manufacturing color filters using the pigment dispersion method, a photosensitive resin composition containing black pigments such as carbon black is first coated onto a transparent substrate. Then, it is dried under reduced pressure using a vacuum drying apparatus, followed by heating and drying using a heated plate. After image exposure and development, it is hardened (cured) by high-temperature treatment at 200°C or higher, thereby forming a matrix (BM). This process is repeated for each color, such as red, green, and blue, to form pixels, thus creating a color filter with BMs and pixels. However, if the heating and drying using the heated plate is not performed uniformly, the following problems arise: film thickness uniformity deteriorates, and uneven development sometimes occurs on the BMs and pixels, especially in overdeveloped areas, where the adhesion of the BMs deteriorates significantly.

[0004] Microfilms (BMs) are typically arranged in a grid, stripe, or mosaic pattern between red, green, and blue pixels to suppress color mixing between pixels, thereby improving contrast or preventing light leakage. Therefore, high light-blocking properties are required for BMs. Furthermore, the edges of the red, green, and blue pixels formed after the BM is formed partially overlap with the BM, and are thus affected by the BM's film thickness, resulting in a step difference in the overlapping area. In this overlapping area, the pixel flatness is compromised, leading to non-uniformity in the gaps between liquid crystal cells or misalignment of the liquid crystals, resulting in reduced display performance. Therefore, in recent years, there has been a particular demand for thinner and thinner BMs, increasing the pigment concentration in the BM to ensure sufficient light-blocking properties even when thin-filmed. If uneven development occurs, the deterioration of the BM's adhesion becomes particularly significant.

[0005] Furthermore, in order to achieve energy saving and extend the battery life of mobile devices, the output of backlights is being reduced, and the finer lines of the BM (microblading element), which serves as the light-shielding component, are being developed to enable high-brightness image display even under such conditions. Also, in recent years, miniaturization has become mainstream in the LCD market, such as for flat panels; however, on the other hand, the demand for high resolution in large-screen televisions is gradually increasing. For these reasons, the demand for high-resolution BMs is gradually increasing, and in recent years, the requirement for BM lines with a linewidth of around 10 μm has changed to the current requirement of BM lines with a linewidth of around 6 to 8 μm.

[0006] Furthermore, during post-exposure development, a longer development time is typically set to remove residues. However, this can lead to the dissolution (insertion) of the BM at the interface with the substrate, making it easier for the BM fine line pattern to peel off. When the pattern linewidth is 10 μm or more, even if an insertion of about 1 to 2 μm occurs on one side of the BM fine line (approximately 2 to 4 μm in total on both sides of the fine line), the fine line adhesion to the substrate can be maintained. However, in fine line patterns with a linewidth of less than 10 μm, the decrease in the adhesion area at the BM / substrate interface is due to the reduction in the adhesion area. Therefore, the decrease in pattern adhesion is significantly increased for every 1 μm reduction in linewidth.

[0007] Against this background, there is a demand for photosensitive resin compositions with excellent fine-line adhesion and developability, and efforts are underway to improve pigment dispersions that affect fine-line characteristics and developability. For example, dispersing agents are known to be used in pigment dispersions. Examples of dispersing agents include compounds containing carboxyl, sulfonic acid, or phosphate groups. From the viewpoint of pigment dispersibility and industrial applicability, compounds containing sulfonic acid groups are sometimes used. For example, Patent Document 1 describes a photosensitive resin composition for color filters in which the developability and residue are improved by using a dispersing agent (containing a sulfonic acid group compound) with an acid value of 0 to 30 in a specific alkali-soluble resin. [Prior Art Documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2008-164937 [Summary of the Invention]

[0009] [The problem the invention aims to solve]

[0010] The inventors conducted a BM evaluation using the photosensitive resin composition described in Patent Document 1, and found that the solubility and fine-line adhesion were not sufficient.

[0011] Therefore, the object of the present invention is to provide a pigment dispersion of a photosensitive resin composition with excellent solubility and fine-line adhesion, and a photosensitive resin composition using the same. [Technical Means for Solving the Problem]

[0012] The inventors conducted intensive research and discovered that the above-mentioned problems could be solved by using a specific compound. The essence of this invention is as follows.

[0013] [1] A pigment dispersion comprising (A) a pigment, (B) a dispersant and (C) a sulfonic acid compound, wherein the conductivity of the (C) sulfonic acid compound is 2000 μS / cm or more and 9000 μS / cm or less, and the acid value of the (C) sulfonic acid compound is 40 mgKOH / g or more. [2] The pigment dispersion of [1] wherein the (C) sulfonic acid compound comprises at least one selected from the group consisting of sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of pyrrolopyrroledione, and sulfonic acid derivatives of diazonium. [3] The pigment dispersion of [1] wherein the (C) sulfonic acid compound comprises a copper phthalocyanine sulfonic acid derivative. [4] The pigment dispersion of any one of [1] to [3], wherein the mass ratio of the pigment (A) to the sulfonic acid compound (C) is 10 or more. [5] The pigment dispersion of any one of [1] to [4], wherein the mass ratio of the pigment (A) to the dispersant (B) is 4 or more. [6] The pigment dispersion of any one of [1] to [5], wherein the pigment (A) contains carbon black. [7] A photosensitive resin composition comprising (A) a pigment, (B) a dispersant, (C) a sulfonic acid-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator, wherein the conductivity of the (C) sulfonic acid-containing compound is 2000 μS / cm or more and 9000 μS / cm or less, and the acid value of the (C) sulfonic acid-containing compound is 40 mgKOH / g or more. [8] The photosensitive resin composition of [7] wherein the (C) sulfonic acid-containing compound comprises at least one selected from the group consisting of sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of pyrrolopyrroledione, and sulfonic acid derivatives of diazonium. [9] The photosensitive resin composition of [7] wherein the (C) sulfonic acid-containing compound comprises a copper phthalocyanine sulfonic acid derivative.

[10] A photosensitive resin composition of any one of [7] to [9], wherein the pigment (A) contains carbon black.

[11] A curing agent formed by curing the photosensitive resin composition of any one of [7] to

[10] .

[12] A black matrix comprising the curing agent of

[11] .

[13] An image display device having the curing agent of

[11] . [Effects of the Invention]

[0014] According to the present invention, a pigment dispersion that yields a photosensitive resin composition with excellent solubility and fine-line adhesion, and a photosensitive resin composition using the same, can be provided.

Implementation Method

[0016] Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments and can be implemented with various modifications within its scope. Furthermore, in the present invention, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acrylic acid".

[0017] In this invention, "total solids content" refers to all components, excluding the solvent, contained in the photosensitive resin composition or pigment dispersion, even if the components excluding the solvent are liquid at room temperature, they are still included in the solids content. In this invention, the weight-average molecular weight refers to the weight-average molecular weight (Mw) of polystyrene obtained by GPC (gel permeation chromatography). In this invention, unless otherwise specified, "amine value" represents the amine value converted from the effective solids content, which is expressed as the amount of bases per 1 g of the solids content of the dispersant and the mass of the equivalent KOH. Furthermore, the determination method is as follows. In this invention, the acid value represents the acid value converted from the effective solids content, which is calculated by neutralization titration.

[0018] [Pigment Dispersion] The pigment dispersion of the present invention contains (A) a pigment, (B) a dispersant, and (C) a sulfonic acid-containing compound, characterized in that: the conductivity of the sulfonic acid-containing compound (C) is 2000 μS / cm or more and 9000 μS / cm or less, and the acid value of the sulfonic acid-containing compound (C) is 40 mgKOH / g or more. By using sulfonic acid-containing compounds that are adjusted or combined to form specific conductivity and acid values, when preparing photosensitive resin compositions using the pigment dispersion of the present invention, photosensitive resin compositions with excellent solubility and fine-line adhesion can be obtained.

[0019] The pigment dispersion of the present invention may also contain other components as needed, such as solvents, alkali-soluble resins, and dyes. Regarding solvents and alkali-soluble resins, the solvents and alkali-soluble resins used in the photosensitive resin compositions of the present invention described below may be appropriately used.

[0020] <(A) Pigment> The pigment dispersion of the present invention comprises (A) pigment. (A) pigment refers to that which colors the pigment dispersion and photosensitive resin composition of the present invention.

[0021] (A) As a pigment, pigments of various colors such as blue, green, red, yellow, purple, orange, brown, and black can be used. Furthermore, as for its structure, in addition to organic pigments such as azo, phthalocyanine, quinacrine, benzimidazolone, isoindolinone, diazonium, indigo, and perylene pigments, various inorganic pigments can also be used.

[0022] Hereinafter, specific examples of pigments that can be used in this invention will be indicated by pigment designations. Furthermore, the terms "CI Pigment Red 2" and similar terms listed below refer to the Color Index (CI). Examples of red pigments include: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147,1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 23 2, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, a preferred example is CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and further preferred examples are CI Pigment Red 177, 209, 224, 254.

[0023] As a blue pigment, examples include: CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 are preferred examples, and CI Pigment Blue 15:6, 60 are even more preferred examples.

[0024] As a green pigment, examples include: CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. Among these, CI pigment green 7, 36, 58, and 59 are preferred examples.

[0025] As a yellow pigment, examples include: CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 13 3, 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, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferred examples are CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, and even more preferred examples are CI pigment yellow 83, 138, 139, 150, 180, and 185.

[0026] As an orange pigment, examples include: CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, CI pigment orange 38, 64, and 71 are preferred examples.

[0027] As a purple pigment, examples include: CI pigment purple 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, 50. Among these, CI pigment purple 19, 23, and 29 are preferred examples, and CI pigment purple 23 and 29 are even more preferred examples.

[0028] Furthermore, when the photosensitive resin composition using the pigment dispersion of the present invention is a photosensitive resin composition for the black matrix of a color filter, a black pigment can be used as pigment (A). The black pigment can be used alone or mixed with red, green, blue, etc. Furthermore, these pigments can be appropriately selected from inorganic or organic pigments. Examples of pigments that can be mixed and used in the preparation of black pigments include: Victoria Blue (42595), Golden Amine O (41000), Anionic Brilliant Yellow (Basic 13), Rose Red 6GCP (45160), Rose Red B (45170), Safranbolu OK 70:100 (50240), Wool Poppy Red X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Smüller Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Smüller Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fastogen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red. GD (pigment red 168), Leonor Green 2YS (pigment green 36) (Furthermore, the numbers in parentheses above refer to the color index (CI)).

[0029] Furthermore, regarding other pigments that can be mixed, if represented by CI numbers, examples include: CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61, 64; CI red pigments 9, 97, 122, 12... 3, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, CI Purple Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64, CI Green Pigment 7, CI Brown Pigment 23, 25, 26.

[0030] Furthermore, examples of black pigments that can be used alone include: carbon black, acetylene black, lampblack, bone black, graphite, iron black, aniline black, indigo black, titanium black, perylene black, and acetylene black. When using a black pigment among these (A) pigments, from the viewpoint of opacity and image characteristics, the aforementioned black pigments that can be used alone are preferred, and carbon black is particularly preferred. Examples of carbon black include the following.

[0031] Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MD120, MD130, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #95 0, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150 , #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Manufactured by Degussa: Printex (registered trademark, same below) 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Cabot manufactures: Monarch (registered trademark, same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark,(The following are the same) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8 Manufactured by Birla: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAV EN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000,

[0032] Furthermore, as pigments, barium sulfate, lead sulfate, titanium dioxide, litharge, iron oxide, and chromium oxide may also be used, for example. Multiple of these pigments may also be used together. For example, to adjust chromaticity, green pigment may be used in combination with yellow pigment, or blue pigment may be used in combination with purple pigment.

[0033] The average particle size of the pigment (A) used in this invention, for example in the case of manufacturing a black matrix of a color filter, is not particularly limited as long as it can achieve the desired color rendering, but varies depending on the type of pigment used. Preferably, it is 10 to 100 nm, more preferably 10 to 70 nm. By setting the average particle size of the pigment to the above range, there is a tendency to make the color characteristics of the liquid crystal display device manufactured using the pigment dispersion of this invention of high quality. Furthermore, when the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and more preferably 20 nm or more. For example, preferably 20 to 60 nm, more preferably 20 to 50 nm. By setting the average particle size to the above upper limit value or below, there is a tendency to reduce scattering and suppress the reduction of color characteristics such as light-blocking properties and contrast. Furthermore, by setting the average particle size to the above lower limit value or above, there is a tendency to achieve good dispersibility without excessive amount of dispersant. Furthermore, the average particle size of the aforementioned pigment can be determined by directly measuring the size of primary particles from electron microscope images. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and their average value is taken as the particle size. Then, for more than 100 particles, the volume (mass) of each particle is approximated by a cuboid of the determined particle size, and the volume average particle size is calculated and taken as the average particle size. Moreover, the same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0034] Furthermore, in addition to pigment (A), the pigment dispersion of the present invention may also incorporate dyes within a range that does not affect the effects of the present invention. Examples of dyes that can be incorporated include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene dyes.

[0035] As azo dyes, examples include: CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7.

[0036] Examples of anthraquinone dyes include: CI Variant Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0037] In addition, examples of phthalocyanine dyes include CI Vat Blue 5, examples of quinone imine dyes include CI Basic Blue 3 and CI Basic Blue 9, examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

[0038] The photosensitive resin composition using the pigment dispersion of the present invention can be used for various applications, and its excellent image forming properties are particularly effective when used to form a black matrix for color filters. When used to form a black matrix, as pigment (A), the aforementioned black pigments such as carbon black or titanium black can be used, or a mixture of several pigments other than black can be used to adjust to black. Among these, carbon black is particularly preferred from the viewpoint of dispersion stability and light-blocking properties.

[0039] The photosensitive resin composition of the present invention exhibits a greater effect on fine line adhesion in regions where the pigment concentration increases. Especially in recent years, it has become necessary to increase pigment concentration to improve opacity. In regions where the effect is increased as described above, the pigment content (A) relative to the total solids content of the photosensitive resin composition is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 52% by mass or more. Furthermore, from the viewpoint of image forming performance, it is preferably 70% by mass or less, more preferably 65% ​​by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 30-70% by mass, more preferably 40-70% by mass, and even more preferably 50-65% by mass, and even more preferably 52-65% by mass.

[0040] In the photosensitive resin composition of the present invention, by setting the pigment content ratio within the above-mentioned range, a photosensitive resin composition with higher opacity (optical concentration, OD value) can be obtained. Specifically, by setting the content ratio of pigment (A) relative to the total solids content of the photosensitive resin composition to 50% by mass or more, the optical concentration when forming a black matrix with a thickness of 1 μm using the photosensitive resin composition of the present invention can be 4.0 or more. The optical concentration is more preferably 4.1 or more, and even more preferably 4.2 or more. In areas with higher opacity, pattern peeling due to development is easily observed, but when using a photosensitive resin composition utilizing the pigment dispersion of the present invention, especially when the content ratio of pigment (A) is higher, the fine line bonding effect of the present invention can be well confirmed.

[0041] In the photosensitive resin composition of the present invention, the content ratio of (A) pigment is not particularly limited. In 100 parts by weight of (D) alkali-soluble resin, it is preferably 20 parts by weight or more, more preferably 50 parts by weight or more, further preferably 100 parts by weight or more, further preferably 120 parts by weight or more, further preferably 150 parts by weight or more, particularly preferably 180 parts by weight or more, and preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and further preferably 250 parts by weight or less. By setting the content ratio of (A) pigment to the above-mentioned lower limit or above, it is easier to suppress the decrease in solubility of the unexposed portion in the developer. Furthermore, by setting it to the above-mentioned upper limit or below, it is more likely to improve the fine line adhesion during development. The above-mentioned upper and lower limits can be arbitrarily combined. For example, the preferred amount is 20 to 500 parts by weight, more preferably 50 to 500 parts by weight, further preferably 100 to 300 parts by weight, further preferably 120 to 300 parts by weight, further preferably 150 to 250 parts by weight, and even more preferably 180 to 250 parts by weight.

[0042] <(B) Dispersant> The pigment dispersion of the present invention includes a (B) dispersant because finely dispersing (A) pigment and stabilizing its dispersion state are important for ensuring quality stability. As the (B) dispersant, a polymeric dispersant with functional groups is preferred. Furthermore, in terms of dispersion stability, a polymeric dispersant with functional groups such as carboxyl groups, phosphate groups, sulfonic acid groups, or such bases; primary, secondary, or tertiary amine groups; quaternary ammonium groups; or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyridine is preferred. Among these, a polymeric dispersant with basic functional groups such as primary, secondary, or tertiary amine groups; quaternary ammonium groups; or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyridine is particularly preferred. By using a polymeric dispersant with such basic functional groups, good dispersibility is achieved, and higher opacity is tended to be attained.

[0043] Furthermore, examples of polymeric dispersants include: carbamate dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers and macromonomers having amine groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0044] Specific examples of such dispersants include: trade names such as EFKA (registered trademark, manufactured by EFKA CHEMICALS BV (EFKA) Co., Ltd.), Disperbyk (registered trademark, manufactured by BYK-Chemie Co., Ltd.), Disparlon (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Flowlen (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Ltd.). These polymeric dispersants can be used alone or in combination of two or more.

[0045] Of these, in terms of fine line cohesion and linearity, it is particularly preferred to use a urethane-based polymeric dispersant and / or an acrylic polymeric dispersant containing basic functional groups as (B) dispersant. In terms of fine line cohesion, a urethane-based polymeric dispersant is particularly preferred. Furthermore, in terms of dispersibility and shelf life, a polymeric dispersant containing basic functional groups and polyester and / or polyether bonds is more preferred.

[0046] The weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or higher, more preferably 1000 or higher, and preferably 100,000 or lower, more preferably 50,000 or lower, and even more preferably 30,000 or lower. By setting it below the above upper limit, there is a tendency for alkaline developability to become good even at higher pigment concentrations. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 700 to 100,000, more preferably 700 to 50,000, and even more preferably 1000 to 30,000. Examples of urethane and acrylic polymeric dispersants include: Disperbyk 160-167, 182 series (all urethane), Disperbyk 2000, 2001, etc. (all acrylic) (all manufactured by BYK-Chemie). Among the above-mentioned urethane-based polymeric dispersants having basic functional groups and polyester and / or polyether bonds, those with a weight average molecular weight of 30,000 or less are particularly preferred, for example Disperbyk 167 and 182.

[0047] <Carbamate-based polymeric dispersants> Examples of carbamate-based polymeric dispersants include dispersion resins with a weight average molecular weight of 1,000 to 200,000 obtained by reacting polyisocyanate compounds, compounds having one or two hydroxyl groups in the molecule with a number average molecular weight of 300 to 10,000, and compounds having active hydrogen and tertiary amine groups in the same molecule.

[0048] Examples of the above-mentioned polyisocyanate compounds include: aromatic diisocyanates such as terephthalic diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and bitoluidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isoflavone diisocyanate, 4,4'-methylenebis(cyclohexyl) isocyanate, and ω,ω'-diisocyanate. Alicyclic diisocyanates such as dimethylcyclohexane cyanate; aliphatic diisocyanates with aromatic rings such as phenyl diisocyanate and α,α,α',α'-tetramethylphenyl diisocyanate; triisocyanates such as lysine triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyano-4-isocyanomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tris(isocyanophenylmethane), tris(isocyanophenyl) thiophosphate, and their trimers, hydrates, and polyol adducts. As polyisocyanates, trimers of organic diisocyanates are preferred, and most preferably trimers of toluene diisocyanate and isoflavone diisocyanate. One of these may be used alone, or two or more may be used in combination.

[0049] As a method for manufacturing isocyanate trimers, the following method can be cited: For the above-mentioned polyisocyanates, a suitable trimerizing catalyst, such as a tertiary amine, phosphine, alkoxide, metal oxide, carboxylate, etc., is used to locally trimerize the isocyanate group. After the trimerization is stopped by adding a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the target polyisocyanate containing isocyanuric acid group.

[0050] Examples of compounds having one or two hydroxyl groups in the same molecule with an average molecular weight of 300 to 10,000 include: polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and compounds formed by alkoxylation of one of the terminal hydroxyl groups of such compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more such compounds.

[0051] Examples of polyether glycols include polyether glycols, polyether ester glycols, and mixtures of two or more thereof. Examples of polyether glycols include those obtained by copolymerizing epoxides alone or in combination, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more thereof.

[0052] Examples of polyether diols include those obtained by reacting an ether-containing diol or a mixture of other diols with a dicarboxylic acid or an anhydride thereof, or by reacting an epoxide with a polyester diol, such as poly(polyoxytetramethylene) adipate. Preferably, polyethylene glycol, polypropylene glycol, polyoxytetramethylene diol, or compounds formed by alkoxylating a terminal hydroxyl group of one of these compounds with an alkyl group having 1 to 25 carbon atoms.

[0053] Examples of polyester diols include: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides reacting with diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentanediol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol). Polyols obtained by polycondensation of aliphatic diols such as alcohols, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylenediol, 2-methyl-1,8-octamethylenediol, and 1,9-nonanediol, alicyclic diols such as dihydroxymethylcyclohexane, aromatic diols such as benzenediethanol and dihydroxyethoxybenzene, and N-alkyldialkylolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene adipate / propylene adipate, or polylactone diols or monohydric alcohols obtained by using the above-mentioned diols or a monohydric alcohol having 1 to 25 carbon atoms as a starting agent, such as polycaprolactone diol, polymethylvalerol, and mixtures of two or more of the above. Polycaprolactone diol or polycaprolactone having an alcohol having 1 to 25 carbon atoms as a starting agent is preferred as the polyester diol.

[0054] Examples of polycarbonate diols include: poly(1,6-hexyl) carbonate, poly(3-methyl-1,5-pentyl) carbonate, etc. Examples of polyolefin diols include: polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. One of these can be used alone, or two or more can be used in combination.

[0055] The average molecular weight of compounds having one or two hydroxyl groups within the same molecule is preferably 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.

[0056] The compounds containing an active hydrogen and a tertiary amino group within the same molecule used in this invention will be described. The active hydrogen, i.e., the hydrogen atom directly bonded to an oxygen, nitrogen, or sulfur atom, can be exemplified by hydrogen atoms in functional groups such as hydroxyl, amino, and thiol groups, with amino groups, especially primary amino groups, being preferred. The tertiary amino group is not particularly limited; examples include amino groups having alkyl groups with 1 to 4 carbon atoms, or heterocyclic structures. More specifically, imidazole rings or triazole rings are examples. Examples of compounds containing both active hydrogen and tertiary amine groups within the same molecule include: N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0057] Furthermore, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of such nitrogen-containing heterocycles include: pyrazole rings, imidazole rings, triazole rings, tetraazole rings, indole rings, carbazole rings, indazole rings, benzimidazole rings, benzotriazole rings, benzothiazole rings, benzothiazolium rings, benzothiadiazole rings, and other nitrogen-containing 5-membered heterocycles; pyridine rings, pyrazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings, isoquinoline rings, and other nitrogen-containing 6-membered heterocycles. Among these nitrogen-containing heterocycles, imidazole rings or triazole rings are preferred.

[0058] Examples of compounds having an imidazole ring and an amino group include: 1-(3-aminopropyl)imidazolium, histidine, 2-aminoimidazolium, and 1-(2-aminoethyl)imidazolium. Examples of compounds having a triazole ring and an amino group include: 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole are preferred. One of these can be used alone, or two or more can be used in combination.

[0059] When manufacturing carbamate-based polymeric dispersants, the mixing ratio of raw materials relative to 100 parts by mass of the polyisocyanate compound is preferably 10 to 200 parts by mass of compounds having one or two hydroxyl groups per molecule with an average molecular weight of 300 to 10,000, more preferably 20 to 190 parts by mass, and even more preferably 30 to 180 parts by mass of compounds having active hydrogen and tertiary amine groups per molecule, and preferably 0.2 to 25 parts by mass of compounds having active hydrogen and tertiary amine groups per molecule, more preferably 0.3 to 24 parts by mass.

[0060] The manufacture of the urethane-based polymeric dispersant is carried out according to a known method for manufacturing polyurethane resin. Solvents used in the manufacture include, for example: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and acetic acid solvents; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, dibutanol, and tert-butanol; chlorides such as dichloromethane and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. One of these solvents may be used alone, or two or more may be used in combination.

[0061] In the above-described manufacturing process, an aminocarbamate reaction catalyst may also be used. Examples of such catalysts include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctanoate, and stannous octoate; iron-based catalysts such as ferric acetopyruvate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine. One of these catalysts may be used alone, or two or more may be used in combination.

[0062] <Method for Determination of Amine Value> The amine value of a dispersant is expressed as the amount of bases per 1 g of solid components (excluding solvent) in the dispersant sample and the equivalent mass of KOH. It can be determined by the following method. Accurately weigh 0.5 to 1.5 g of the dispersant sample and place it in a 100 mL beaker. Dissolve it in 50 mL of acetic acid. Use an automatic titration apparatus equipped with a pH electrode and neutralize and titrate the solution with 0.1 mol / L HClO4 (perchloric acid) acetic acid solution. Take the inflection point of the titration pH curve as the titration endpoint and calculate the amine value using the following formula. Amine value [mgKOH / g]=(561×V) / (W×S) [where, W: represents the amount of dispersant sample weighed [g], V: represents the titration amount at the titration endpoint [mL], S: represents the concentration of solid components in the dispersant sample [mass%]].

[0063] The amount of compound containing both active hydrogen and tertiary amine groups within the same molecule, expressed as the amine value after the reaction, is preferably controlled to be 1–100 mg KOH / g. More preferably, it is 5–95 mg KOH / g. The amine value is a value obtained by titrating the neutralization of a basic amine group with an acid, corresponding to the acid value, and expressed in mg of KOH. By setting the amine value above the aforementioned lower limit, there is a tendency for improved dispersibility; conversely, by setting it below the aforementioned upper limit, there is a tendency for improved developability.

[0064] Furthermore, when isocyanate groups remain in the polymeric dispersant during the above reaction, if the isocyanate groups are further consumed using an alcohol or amine compound, the stability of the product over time is improved, which is preferable. The weight-average molecular weight (Mw) of the carbamate-based polymeric dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. The weight-average molecular weight (Mw) of the carbamate-based polymeric dispersant is particularly preferably 30,000 or less. For example, it is preferably 1,000 to 30,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 30,000. By setting it to the lower limit or above, there is a tendency for improved dispersibility and dispersion stability; by setting it to the upper limit or below, there is a tendency for improved solubility. If the molecular weight is below 30,000, there is a tendency for alkaline developability to become good even when the pigment concentration is particularly high. Examples of commercially available carbamate dispersants that are particularly good in this regard include Disperbyk 167 and 182 (manufactured by BYK-Chemie).

[0065] In the pigment dispersion of the present invention, the content ratio ((A) pigment to (B) dispersant, based on mass ((A) pigment / (B) dispersant)) is preferably 1 or more, more preferably 3 or more, further preferably 4 or more, and even more preferably 5 or more. It is also preferably 50 or less, further preferably 30 or less, and even more preferably 15 or less. By setting it to the lower limit or above, there is a tendency for improved developing solubility. Furthermore, by setting it to the upper limit or below, there is a tendency for improved dispersion stability. The upper and lower limits can also be arbitrarily combined. For example, it is preferably 1 to 50, more preferably 3 to 50, further preferably 4 to 30, and even more preferably 5 to 15.

[0066] The content ratio of the dispersant (B) in the photosensitive resin composition of the present invention is not particularly limited. In the total solids content of the photosensitive resin composition, it is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less; furthermore, it is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass. Furthermore, in the photosensitive resin composition of the present invention, the content ratio of the dispersant (B) relative to 100 parts by mass of pigment (A) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, and preferably 200 parts by mass or less, even more preferably 80 parts by mass or less, and even more preferably 50 parts by mass or less. By setting it to the above-mentioned lower limit or above, there is a tendency to easily ensure sufficient dispersibility. Furthermore, by setting it to the above-mentioned upper limit or below, there is a tendency to easily achieve sufficient color concentration, sensitivity, film-forming properties, etc., without reducing the ratio of other components. The above-mentioned upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 200 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 15 to 50 parts by mass.

[0067] <(C) Sulfonic Acid Compound> To improve dispersibility and shelf life, the pigment dispersion of the present invention contains a (C) sulfonic acid compound. Examples of (C) sulfonic acid compounds include: azo compounds, phthalocyanine compounds, quinacrine compounds, benzimidazolone compounds, quinacrine compounds, isoindolineone compounds, diazonium compounds, anthraquinone compounds, indanthrine compounds, perylene compounds, violet ketone compounds, pyrrolopyrrole dione compounds, and derivatives of diazonium compounds. Among these, derivatives of phthalocyanine compounds and quinacrine compounds are preferred.

[0068] (C) Examples of compounds containing a sulfonic acid group include compounds having a sulfonic acid group, and other substituents such as sulfonamide and its quaternary salt, phthalimide methyl, dialkylamino alkyl, hydroxyl, carboxyl, and amide groups may be directly or indirectly bonded to the skeleton of the compound via, for example, alkyl, aryl, or heterocyclic groups. (C) Preferably, compounds containing a sulfonic acid group are those in addition to a sulfonic acid group, where other substituents such as sulfonamide and its quaternary salt, phthalimide methyl, dialkylamino alkyl, hydroxyl, carboxyl, and amide groups are directly or indirectly bonded to the skeleton of the compound via, for example, alkyl, aryl, or heterocyclic groups. These other multiple substituents may also substitute for one skeleton of the compound. (C) The sulfonic acid-containing compound is preferably a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of pyrrolopyrroledione, or a sulfonic acid derivative of dichlorophenate, more preferably a sulfonic acid derivative of phthalocyanine, and even more preferably a copper phthalocyanine sulfonic acid derivative. Furthermore, as the sulfonic acid-containing compound (C), it is preferably a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of pyrrolopyrroledione, or a sulfonic acid derivative of dichlorophenate, more preferably a sulfonic acid derivative of phthalocyanine, and even more preferably a copper phthalocyanine sulfonic acid derivative. One of these compounds may be used alone, or two or more may be used in combination.

[0069] The content ratio of the (C) sulfonic acid compound contained in the pigment dispersion of the present invention is not particularly limited. Preferably, it is 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 preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5.0% by mass or less. By setting it to the lower limit or above, there is a tendency to improve dispersion stability. Furthermore, by setting it to the upper limit or below, there is a tendency to suppress pigment aggregation and make the coating surface more uniform.

[0070] In the pigment dispersion of the present invention, the mass ratio ((A) pigment to (C) sulfonic acid compound) is preferably 10 or more, more preferably 20 or more, and even more preferably 25 or more. It is also preferably 200 or less, more preferably 150 or less, more preferably 100 or less, and even more preferably 50 or less. By setting the value to the lower limit or above, there is a tendency to improve substrate adhesion. Furthermore, by setting the value to the upper limit or below, there is a tendency to improve dispersion stability. The upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 200, more preferably 10 to 150, more preferably 20 to 100, and even more preferably 25 to 50.

[0071] The content ratio of the (C) sulfonic acid compound included in the photosensitive resin composition of the present invention is not particularly limited. Relative to the total solids content of the photosensitive resin composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, and preferably 10% by mass or less, and even more preferably 5% by mass or less. By setting it to the lower limit or above, there is a tendency to improve developability and solubility. Furthermore, by setting it to the upper limit or below, there is a tendency to improve developability and pattern adhesion. The upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1.0 to 5% by mass.

[0072] <Method for Determining Conductivity> (C) The conductivity of the sulfonic acid-containing compound is 2000 μS / cm or more and 9000 μS / cm or less. The conductivity of the sulfonic acid-containing compound is expressed as the conductivity when the sulfonic acid-containing compound is stirred in ultrapure water to form a 5% solution, and can be measured using a conductivity meter. The unit can be recorded in μS / cm. The conductivity of the sulfonic acid-containing compound is 2000 μS / cm or more, preferably 2500 μS / cm or more, more preferably 3000 μS / cm or more, and 9000 μS / cm or less, preferably 8000 μS / cm or less, more preferably 7000 μS / cm or less. By setting it to the lower limit or above, there is a tendency to improve dispersion stability. Furthermore, by setting it to the upper limit or below, there is a tendency to suppress undercutting and improve development adhesion. The upper and lower limits can be combined arbitrarily. For example, the value is 2000–9000 μS / cm, preferably 2500–8000 μS / cm, and even more preferably 3000–7000 μS / cm.

[0073] (C) The acid value of the sulfonic acid compound is 40 mgKOH / g or higher, preferably 60 mgKOH / g or higher, more preferably 80 mgKOH / g or higher, even more preferably 90 mgKOH / g or higher, particularly preferably 100 mgKOH / g or higher, and preferably 500 mgKOH / g or lower, more preferably 300 mgKOH / g or lower, even more preferably 200 mgKOH / g or lower, and even more preferably 150 mgKOH / g or lower. By setting the value to the lower limit or higher, there is a tendency for increased solubility. Furthermore, by setting the value to the upper limit or lower, there is a tendency for improved adhesion of fine lines while suppressing undercutting. The upper and lower limits can be combined arbitrarily. For example, the preferred concentration is 40–500 mgKOH / g, more preferably 60–500 mgKOH / g, further preferably 80–300 mgKOH / g, further preferably 90–200 mgKOH / g, and even more preferably 100–150 mgKOH / g.

[0074] The pigment dispersion of the present invention is used, for example, in a state in which (A) pigment, (B) dispersant and (C) sulfonic acid compound and various materials as needed are dissolved or dispersed in a solvent. As a solvent, water or the organic solvent used in the photosensitive resin composition of the present invention described below can be used appropriately.

[0075] When the pigment dispersion of the present invention contains an organic solvent, the content ratio of the organic solvent is not particularly limited. From the viewpoint of ease of application and viscosity stability, the total solids content in the pigment dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and even more preferably 35% by mass or less. By setting it to the above-mentioned lower limit value or above, there is a tendency to improve the tinting strength and easily improve the optical density (OD value). Furthermore, by setting it to the above-mentioned upper limit value or below, there is a tendency to improve the dispersion stability. The above-mentioned upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, further preferably 10 to 40% by mass, and even more preferably 20 to 35% by mass.

[0076] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention comprises (A) a pigment, (B) a dispersant, (C) a sulfonic acid-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator. Its characteristic is that the conductivity of the sulfonic acid-containing compound (C) is 2000 μS / cm or more and 9000 μS / cm or less, and the acid value of the sulfonic acid-containing compound (C) is 40 mgKOH / g or more. By using sulfonic acid-containing compounds that are adjusted or combined to form specific conductivity and acid values, a photosensitive resin composition with excellent solubility and fine-line adhesion can be obtained.

[0077] As the pigment (A), dispersant (B), and sulfonic acid compound contained in the photosensitive resin composition of the present invention, the pigment (A), dispersant (B), and sulfonic acid compound (C) exemplified in the above-mentioned pigment dispersion can be appropriately used.

[0078] <(D) Alkali-soluble resin> As the (D) alkali-soluble resin, it is not particularly limited as long as it is one in which the solubility of the exposed and unexposed portions of the coating obtained by coating and drying the photosensitive resin composition changes after exposure. Preferably, it is an alkali-soluble resin having carboxyl groups. Furthermore, it is more preferably an alkali-soluble resin having vinyl unsaturated groups, and even more preferably an alkali-soluble resin having both vinyl unsaturated groups and carboxyl groups. An example is shown below.

[0079] <Alkali-soluble resin (d1)> Preferably, the alkali-soluble resin (D) in this invention comprises an alkali-soluble resin (d1) having a partial structure represented by the following general formula (d1-1). By including the alkali-soluble resin (d1), there is a tendency for improved adhesion.

[0080] [Chemical 1]

[0081] The benzene ring in formula (d1-1) can also be substituted by any substituents. R7 independently represents a hydrogen atom or a methyl group. X independently represents O, S, CO or a direct bond. * represents a bonded bond. n represents an integer from 0 to 4.

[0082] In the above general formula (d1-1), from the point of view of sensitivity, n is preferably 3 or less, more preferably 2 or less, and even more preferably 0. R7 is preferably a hydrogen atom.

[0083] In the above general formula (d1-1), from the point of view of sensitivity, X is preferably a direct bond.

[0084] The alkali-soluble resin (d1) having a partial structure represented by formula (d1-1) is preferably an alkali-soluble resin obtained by adding (meth)acrylic acid to an epoxy resin having a Cardo skeleton represented by formula (d7-1), and then reacting it with a polybasic acid and / or its anhydride.

[0085] [Chemical 2]

[0086] The benzene ring in formula (d7-1) can also be substituted by any substituent. X independently represents O, S, CO, or a direct bond. n represents an integer from 0 to 4.

[0087] In the above general formula (d7-1), n ​​represents an integer from 0 to 4, and n is preferably 3 or less, more preferably 2 or less, and even more preferably 0.

[0088] As a method for the addition reaction of (meth)acrylic acid with epoxy resin, a known method may be used. For example, the reaction may be carried out in the presence of an esterification catalyst at a temperature of 50–150°C. As the catalyst used herein, tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine; tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride may be used.

[0089] The amount of (meth)acrylic acid used is preferably in the range of 0.5 to 1.2 equivalents relative to the epoxy groups of the epoxy resin, and more preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of (meth)acrylic acid used above the lower limit mentioned above, the amount of unsaturated groups introduced becomes sufficient, and the subsequent reaction with polybasic acids and / or their anhydrides also becomes sufficient. Furthermore, the tendency for a large amount of epoxy groups to remain is suppressed. On the other hand, by setting the amount used below the upper limit mentioned above, the tendency for (meth)acrylic acid to remain as an unreacted substance is suppressed.

[0090] As a polybasic acid and / or its anhydride, examples may be selected from one or more of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloric acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and the anhydrides of such acids.

[0091] Regarding the addition reaction of polybasic acids and / or their anhydrides, known methods can also be used to continue the reaction under the same conditions as the addition reaction of (meth)acrylic acid to obtain the target product.

[0092] When synthesizing alkali-soluble resin (d1) by addition reaction of polybasic acid and / or its anhydride, polyols such as trimethylolpropane, pentaerythritol, and dipentaerythritol can also be added to introduce multi-branched structures.

[0093] The alkali-soluble resin (d1) is obtained, for example, by heating a mixture of a polybasic acid and / or its anhydride in a reactant of epoxy resin and (meth)acrylic acid, or by mixing a polybasic acid and / or its anhydride and a polyol in a reactant of epoxy resin and (meth)acrylic acid. In this case, there is no particular restriction on the order of mixing the polybasic acid and / or its anhydride with the polyol. Heating causes the polybasic acid and / or its anhydride to undergo an addition reaction with any hydroxyl group present in the mixture of the reactant of (meth)acrylic acid and the polyol.

[0094] From the viewpoint of inhibiting thickening and gelation and exhibiting an effect, the amount of polyol used is usually about 0.01 to 0.5 times by mass relative to the reactants of epoxy resin and (meth)acrylic acid and the reactants of polyacid and / or its anhydride, preferably about 0.02 to 0.2 times by mass.

[0095] Alkali-soluble resin (d1) can be used alone or in combination with two or more resins.

[0096] The acid value of the alkali-soluble resin (d1) is preferably 10 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, even more preferably 80 mgKOH / g or higher, and preferably 200 mgKOH / g or lower, even more preferably 150 mgKOH / g or lower, and even more preferably 120 mgKOH / g or lower. By setting it to the lower limit or above, there is a tendency to reduce residue. Furthermore, by setting it to the upper limit or below, there is a tendency to achieve good bonding of fine threads. The upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 200 mgKOH / g, more preferably 50 to 200 mgKOH / g, even more preferably 80 to 150 mgKOH / g, and even more preferably 80 to 120 mgKOH / g.

[0097] The weight-average molecular weight (Mw) of the alkali-soluble resin (d1), as measured by gel permeation chromatography (GPC) of polystyrene, is preferably 1000 or more, more preferably 2000 or more, further preferably 4000 or more, and even more preferably 5000 or more. It is also preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, further preferably 8000 or less, and even more preferably 7000 or less. Setting the value to the lower limit or above tends to improve the tightness of the fine lines. Furthermore, setting the value to the upper limit or below tends to improve the solubility or redissolution properties during development. The upper and lower limits can be arbitrarily combined. For example, the value is preferably 1,000 to 20,000, more preferably 1,000 to 15,000, even more preferably 2,000 to 10,000, even more preferably 4,000 to 8,000, and even more preferably 5,000 to 7,000.

[0098] The photosensitive resin composition of the present invention may also contain an alkali-soluble resin other than the alkali-soluble resin (d1) as (D) the alkali-soluble resin. As for the alkali-soluble resin other than the alkali-soluble resin (d1), it is not particularly limited as long as it is a resin whose solubility in alkaline development changes between the exposed and unexposed areas after exposure to the coating obtained by coating the photosensitive resin composition and drying. Preferably, it is an alkali-soluble resin having carboxyl groups. Furthermore, it is preferably a resin having vinyl unsaturated groups, and even more preferably an alkali-soluble resin having both vinyl unsaturated groups and carboxyl groups. Specifically, examples include epoxy (meth)acrylate resin (d2) with carboxyl groups other than the alkali-soluble resin (d1), acrylic copolymer resin (d3), and other resins (d4).

[0099] <Other than alkali-soluble resin (d1) containing carboxyl groups, epoxy (meth)acrylate resin (d2)> Examples of epoxy (meth)acrylate resin (d2) containing carboxyl groups other than alkali-soluble resin (d1) include epoxy (meth)acrylate resin (d2-1) and epoxy (meth)acrylate resin (d2-2).

[0100] <Epoxy (meth)acrylate resin (d2-1)> An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester with a carboxyl group to an epoxy resin, and then reacting it with a polybasic acid and / or its anhydride.

[0101] <Epoxy (meth)acrylate resin (d2-2)> An alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to an epoxy resin, and then reacting it with a polyol, a polyacid and / or its anhydride.

[0102] <Epoxy (meth)acrylate resin (d2-1), Epoxy (meth)acrylate resin (d2-2)> As a raw material, bisphenol A type epoxy resin (e.g., "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Co., Ltd.) can be used appropriately, as well as epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 7)). 6℃), bisphenol F type resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resins obtained by reacting the alcoholic hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., "NER-7406" (epoxy equivalent 350, softening point 66℃) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resins, biphenyl glycidyl ether (e.g., triphenyl ether, etc.). The following epoxy resins are used: "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.; phenolic varnish-type epoxy resins (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd.; "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Co., Ltd.; "DEN-438" manufactured by Dow Chemical Co., Ltd.); (ortho, meta, and para)cresol phenolic varnish-type epoxy resins (e.g., "EOCN-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.); triglycidyl isocyanate (e.g., "TEPIC" manufactured by Nissan Chemical Co., Ltd.); triphenol methane-type epoxy resins (e.g., "EPPN-501", "EPPN-502", and "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.); alicyclic epoxy resins (e.g., "Celloxide" manufactured by Daicel Corporation). (Registered trademark, hereinafter the same) 2021P, "Celloxide EHPE", epoxy resins obtained by reacting dicyclopentadiene with phenol and then glycidylating them (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (d2-a) to (d2-e). Specifically, for example, as an epoxy resin represented by the following general formula (d2-a), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. can be cited, and as an epoxy resin represented by the following general formula (d2-b), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. can be cited.

[0103] [Chemical 3]

[0104] In formula (d2-a), b11 represents the average value and is a number from 0 to 10. R11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the multiple R11s present in one molecule may be the same or different.

[0105] [Chemical 4]

[0106] In formula (d2-b), b12 represents the average value and is a number from 0 to 10. R21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the plurality of R21s present in one molecule may be the same or different.

[0107] [Chemical 5]

[0108] In formula (d2-c), X represents the linking group represented by the following general formula (d2-c-1) or (d2-c-2). The molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

[0109] [Chemical 6]

[0110] In formulas (d2-c-1) and (d2-c-2), R31 to R34 and R35 to R37 independently represent an adamantyl alkyl group that may have substituents, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, or a phenyl group that may have substituents. Furthermore, the asterisk (*) in the formula indicates a bonding site in (d2-c).

[0111] [Chemistry 7]

[0112] In formula (d2-d), R51 to R54 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, respectively; R55 are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, respectively; and R56 are each independently an alkyl group having 1 to 5 carbon atoms. k is an integer from 1 to 5, l is an integer from 0 to 13, and m is each independently an integer from 0 to 5.

[0113] [Chemical 8]

[0114] In the above general formula (d2-e), n and o are independent integers from 1 to 9. R23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Furthermore, the plurality of R23s present in one molecule may be the same or different.

[0115] Among these, epoxy resins represented by any of the general formulas (d2-a) to (d2-e) are preferred.

[0116] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include: (meth)acrylic acid, butenoic acid, ortho, meta, and p-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substituents at the α-position of (meth)acrylic acid, 2-(meth)acrylic acetoethyl succinic acid, 2-(meth)acrylic acetoethyl adipic acid, 2-(meth)acrylic acetoethyl phthalic acid, 2-(meth)acrylic acetoethyl hexahydrophthalic acid, and 2-(meth)acrylic acetoethyl cis-... Butenedioic acid, 2-(meth)propenyloxypropyl succinic acid, 2-(meth)propenyloxypropyl adipic acid, 2-(meth)propenyloxypropyl tetrahydrophthalic acid, 2-(meth)propenyloxypropyl phthalic acid, 2-(meth)propenyloxypropyl maleic acid, 2-(meth)propenyloxybutyl succinic acid, 2-(meth)propenyloxybutyl adipic acid, 2-(meth)propenyloxybutyl phthalic acid, 2-(meth)propenyloxybutyl phthalic acid, 2-(meth)propenyloxybutyl maleic acid; Examples of (meth)acrylates include monomers having a terminal hydroxyl group, formed by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerol to (meth)acrylate; or (meth)acrylates having a terminal hydroxyl group, formed by adding acids (anhydrides) such as succinic anhydride, phthalic anhydride, and maleic anhydride to monomers such as hydroxyalkyl (meth)acrylates having a terminal hydroxyl group, or compounds such as pentaerythritol tri(meth)acrylate having a terminal hydroxyl group, and having one or more ethylene unsaturated groups and a terminal carboxyl group. (Meth)acrylate dimers are also examples.

[0117] Of these, (meth)acrylic acid is particularly preferred in terms of sensitivity. Known methods can be used as a method for adding α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups to epoxy resin. For example, α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups can be reacted with epoxy resin at a temperature of 50–150°C in the presence of an esterification catalyst. As the catalyst used herein, tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, dimethylbenzylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

[0118] Furthermore, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups, and esterification catalyst can be used individually or in combination. The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups used relative to the epoxy groups of the epoxy resin is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups used to the lower limit or above mentioned above, the amount of unsaturated groups introduced becomes sufficient, the subsequent reaction with polybasic acids and / or their anhydrides becomes sufficient, and the tendency for a large amount of epoxy groups to remain is suppressed. On the other hand, by setting the amount used to the upper limit or below mentioned above, the tendency for α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to remain as unreacted material is suppressed.

[0119] As a polybasic acid and / or its anhydride or polyol, the same compound as that used in the alkali-soluble resin (d1) can be used. Furthermore, the same synthetic method as that used in the alkali-soluble resin (d1) can also be used in the synthesis.

[0120] The acid value of the epoxy (meth)acrylate resin (d2-1, d2-2) obtained as described above is preferably 10 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, and even more preferably 80 mgKOH / g or higher. It is also preferably 200 mgKOH / g or lower, and even more preferably 150 mgKOH / g or lower. By setting the value to the lower limit or above, there is a tendency for improved fine-line adhesion. Furthermore, by setting the value to the upper limit or below, there is a tendency for good development and solubility. The upper and lower limits can be combined arbitrarily. For example, it is preferably 10–200 mgKOH / g, more preferably 50–200 mgKOH / g, and even more preferably 80–150 mgKOH / g.

[0121] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (d2-1, d2-2) converted from polystyrene, as measured by gel permeation chromatography (GPC), is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, and especially preferably 2300 or more. It is also preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, further preferably 8000 or less, and especially preferably 6000 or less. Setting the value to the lower limit or above tends to improve sensitivity, film strength, and alkali resistance. Furthermore, setting the value to the upper limit or below tends to improve developability and resolubility. The upper and lower limits can be arbitrarily combined. For example, the value is preferably 1,000 to 20,000, more preferably 1,000 to 15,000, even more preferably 1,500 to 10,000, even more preferably 2,000 to 8,000, and especially preferably 2,300 to 6,000.

[0122] <Acrylic Copolymer Resin (d3)> As the acrylic copolymer resin (d3), various polymer compounds described in Japanese Patent Application Publication No. 7-207211, Japanese Patent Application Publication No. 8-259876, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-140144, Japanese Patent Application Publication No. 11-174224, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2003-233179, and Japanese Patent Application Publication No. 2007-270147 are preferred. Acrylic copolymer resins (d3-1) to (d3-4) are preferred. Among these, acrylic copolymer resin (d3-1) is particularly preferred.

[0123] Acrylic copolymer resin (d3-1): A resin obtained by adding at least a portion of the epoxy groups of an unsaturated monobasic acid to a copolymer containing epoxy (meth)acrylate and other free radical polymerizable monomers, or by adding at least a portion of the hydroxyl groups generated by the addition reaction to a polybasic acid anhydride. Acrylic copolymer resin (d3-2): A linear, base-soluble resin containing carboxyl groups in its main chain. Acrylic copolymer resin (d3-3): A resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl group portion of the above-mentioned acrylic copolymer resin (d3-2). Acrylic copolymer resin (d3-4): A (meth)acrylic resin.

[0124] <Other Alkali-Soluble Resins (d4)> Other alkali-soluble resins (d4) are any alkali-soluble resins other than alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) and acrylic copolymer resins (d3) that have carboxyl groups. There are no particular restrictions. They can be selected from resins commonly used in photosensitive resin compositions for color filters. For example, alkali-soluble resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, and Japanese Patent Application Publication No. 2007-334290 can be cited.

[0125] (D) The content ratio of the alkali-soluble resin is not particularly limited, but relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting it to the above-mentioned lower limit or above, there is a tendency for the solubility of the unexposed portion in the developer to become better. Furthermore, by setting it to the above-mentioned upper limit or below, there is a tendency for the developer to prevent excessive penetration into the exposed portion, thereby improving the image clarity and fine line adhesion. The above-mentioned upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, even more preferably 10 to 50% by mass, even more preferably 15 to 30% by mass, and especially preferably 20 to 25% by mass.

[0126] In the photosensitive resin composition of the present invention, the content of (D) alkali-soluble resin is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and even more preferably 200 parts by mass or more, relative to 100 parts by mass of the photopolymerizable compound (E). It is also preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 600 parts by mass or less, and particularly preferably 400 parts by mass or less. By reaching the lower limit or above, there is a tendency for the solubility of the unexposed portion in the developer to become better. Furthermore, by reaching the upper limit or below, there is a tendency for excessive penetration of the developer into the exposed portion to be suppressed, resulting in better image clarity and fine line adhesion. The upper and lower limits can be combined arbitrarily. For example, the preferred amount is 100 to 1000 parts by weight, more preferably 100 to 800 parts by weight, even more preferably 150 to 600 parts by weight, and even more preferably 200 to 400 parts by weight.

[0127] <(E) Photopolymerizable Compound> In terms of sensitivity, the photosensitive resin composition of the present invention contains an (E) photopolymerizable compound. Preferably, the (E) photopolymerizable compound is a polyfunctional vinyl monomer having two or more vinyl unsaturated groups per molecule. The number of vinyl unsaturated groups in the polyfunctional vinyl monomer is preferably two or more, more preferably three or more, and even more preferably four or more, and preferably ten or less, even more preferably eight or less. By setting the value to the lower limit or above, the photosensitive resin composition tends to have high sensitivity; conversely, by setting the value to the upper limit or below, the hardening shrinkage during polymerization tends to be smaller. The upper and lower limits can be combined arbitrarily. For example, preferably 2 to 10, more preferably 3 to 10, and even more preferably 4 to 8. Examples of polyfunctional vinyl monomers include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by esterification of aliphatic polyhydroxy compounds, polyhydroxy compounds such as aromatic polyhydroxy compounds, and unsaturated carboxylic acids and polybasic carboxylic acids; preferably, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.

[0128] Examples of esters of the above-mentioned aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, and other aliphatic polyhydroxy compounds; methacrylates obtained by replacing the acrylates of these exemplary compounds with methacrylates; similarly, esters obtained by replacing esters with isocarboxylate, butenolate obtained by replacing esters with butenolate, or maleate obtained by replacing esters with maleate; acrylates of aliphatic polyhydroxy compounds; and methacrylates of aliphatic polyhydroxy compounds.

[0129] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and other aromatic polyhydroxy compounds such as acrylates and methacrylates. Esters obtained through the esterification reaction of polyhydroxy compounds and unsaturated carboxylic acids with polyhydroxy compounds are not necessarily single substances. Representative examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0130] Furthermore, examples of the polyfunctional vinyl monomers used in this invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxy (meth)acrylate or polyisocyanate compound, a polyol, and a hydroxy (meth)acrylate; epoxy acrylates, such as addition reactions of polyepoxides with hydroxy (meth)acrylates or (meth)acrylic acid; acrylamides such as ethyldiacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate. One of these may be used alone, or two or more may be used in combination.

[0131] (E) The content ratio of the photopolymerizable compound is not particularly limited, but relative to the total solids content of the photosensitive resin composition, it is preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and especially preferably 10% by mass or less. By keeping the content of the photopolymerizable compound at or below the above-mentioned upper limit, there is a tendency for the developer to have adequate penetration into the exposed area, resulting in a good image. (E) The lower limit of the content ratio of the photopolymerizable compound is not particularly limited, but it is preferably 1% by mass or more, more preferably 5% by mass or more. By keeping it at or above the above-mentioned lower limit, there is a tendency for photocuring by ultraviolet irradiation to be improved, and the fine line adhesion to also become better. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferred to be 1 to 90% by mass, more preferably 1 to 70% by mass, even more preferably 1 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and especially preferably 5 to 10% by mass.

[0132] <(F) Photopolymerization Initiator> The photosensitive resin composition of the present invention includes a (F) photopolymerization initiator. The (F) photopolymerization initiator is a component that has the function of directly absorbing light, undergoing a decomposition reaction or a hydrogen abstraction reaction to generate polymerizable free radicals. Addition agents such as sensitizing pigments may also be added as needed before use.

[0133] As photopolymerization initiators (F), examples include: metallocene compounds containing dititanium compounds as described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; free radical activators such as halomethylated diazole derivatives, halomethyl-symmetric triazole derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters, and α-aminoalkyl phenyl ketone derivatives as described in Japanese Patent Application Publication No. 2000-80068 and 2006-36750.

[0134] Examples of dicyclopentadienyldichlorotitanium, such as: dicyclopentadienyltitanium biphenyl, bis(2,3,4,5,6-pentafluorobenzyl-1-yl)dicyclopentadienyltitanium, bis(2,3,5,6-tetrafluorobenzyl-1-yl)dicyclopentadienyltitanium, bis(2,4,6-trifluorobenzyl-1-yl)dicyclopentadienyltitanium, bis(2,6-difluorobenzyl-1-yl)dicyclopentadienyltitanium, etc. Benzo-1-yl)dicyclopentadienyl titanium, bis(2,4-difluorobenzo-1-yl)dicyclopentadienyl titanium, bis(2,3,4,5,6-pentafluorobenzo-1-yl)bis(methylcyclopentadienyl) titanium, bis(2,6-difluorobenzo-1-yl)bis(methylcyclopentadienyl) titanium, [2,6-di-fluoro-3-(pyrrolo-1-yl)-benzo-1-yl]dicyclopentadienyl titanium.

[0135] Furthermore, examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0136] Also, examples of halomethylated acediazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-acediazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-acediazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4-acediazole, and 2-trichloromethyl-5-furanyl-1,3,4-acediazole.

[0137] Also, examples of halomethyl-symmetric trihalo derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric trihalo, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric trihalo, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric trihalo, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric trihalo.

[0138] Also, examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminophenylmethylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0139] As a photopolymerization initiator (F), oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) are particularly useful in terms of sensitivity. In cases where the sensitivity becomes unfavorable, such as when using alkali-soluble resins containing phenolic hydroxyl groups, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) with excellent sensitivity are especially useful. Among oxime ester derivatives, oxime ester compounds are preferred from the viewpoint of adhesion to the substrate.

[0140] Oxime ester photopolymerization initiators possess structures that simultaneously absorb ultraviolet light, transmit light energy, and generate free radicals. Therefore, they exhibit high sensitivity in small quantities and are thermally stable, allowing them to be designed into small-quantity, highly sensitive photosensitive resin compositions. This structural characteristic is particularly advantageous when considering the absorption of light at the i-ray (365 nm) of the exposure light source, especially in the case of oxime ester compounds containing substituted carbazole groups (substitutable groups with a carbazole ring). Currently, the market demands high opacity and increasingly higher BM (black matrix) pigment concentrations in films. In such cases, they are particularly effective.

[0141] As an oxime ester compound, examples include compounds containing the structural part represented by the following general formula (22), and more preferably, examples include oxime ester compounds represented by the following general formula (23).

[0142] [Chemical 9]

[0143] In formula (22), R22 represents alkyl with 2 to 12 carbon atoms, heteroarylalkyl with 1 to 20 carbon atoms, alkenyl with 3 to 25 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl with 3 to 20 carbon atoms, aminoalkylcarbonyl with 2 to 10 carbon atoms, aryl with 7 to 20 carbon atoms, heteroaryl with 1 to 20 carbon atoms, alkoxycarbonyl with 2 to 10 carbon atoms, or aryloxycarbonyl with 7 to 20 carbon atoms.

[0144] [Chemical 10]

[0145] In formula (23), R21a represents hydrogen or a substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 3 to 20 carbon atoms, a phenoxycarbonyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonyl group having 1 to 20 carbon atoms, or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 7 to 20 carbon atoms, a heteroaryl 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. R21b represents any substituent containing an aromatic ring or a heteroaryl ring.

[0146] Furthermore, R21a can form a ring together with R21b, and the linking group can be, for example, an alkyl group having 1 to 10 carbon atoms, a polyvinyl group (-(CH=CH)r-), a polyvinylethynyl group (-(C≡C)r-), or a group formed by combining the above (where r is an integer from 0 to 3). R22a represents the same group as R22 in formula (22). Preferably, R22 in formula (22) and R22a in formula (23) are alkyl groups having 2 to 12 carbon atoms, heteroarylalkyl groups having 1 to 20 carbon atoms, or cycloalkyl groups having 3 to 8 carbon atoms.

[0147] As R21a in formula (23), examples are preferably unsubstituted straight-chain alkyl or cycloalkyl groups such as methyl, ethyl, and propyl, or propyl groups substituted with N-acetylated-N-acetylated amino groups. As for R21b in formula (23), examples are preferably substituted carbazole groups, substituted 9-oxothiolated groups, and substituted phenyl thioether groups.

[0148] As a photopolymerization initiator for oxime ester compounds, for the reasons stated above, it is more preferable that R21b in formula (23) is a substituted carbazolyl group. More preferably, it is a carbazolyl group having at least one group selected from the group consisting of substituted aryl groups with 6 to 25 carbon atoms, substituted aryl carbonyl groups with 7 to 25 carbon atoms, substituted heteroaryl groups with 5 to 25 carbon atoms, substituted heteroaryl carbonyl groups with 6 to 25 carbon atoms, and nitro groups. It is particularly preferred that it is a carbazolyl group having at least one group selected from the group consisting of benzoyl, tolyl, naphthyl, thiophenyl carbonyl, and nitro groups. Furthermore, these groups are preferably bonded to the 3-position of the carbazolyl group.

[0149] Commercially available photopolymerization initiators for such oxime ester compounds include OXE-02 manufactured by BASF, TR-PBG-304 or TR-PBG-314 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0150] Specifically, compounds such as those exemplified below can be cited as photopolymerization initiators of oxime ester compounds suitable for the present invention, but are not limited to any of these compounds.

[0151] [Chemical 11]

[0152] [Chemical 12]

[0153] [Chemistry 13]

[0154] As a ketoxime ester compound, examples may be given of compounds containing the structural part represented by the following general formula (24), and more preferably, examples may be given of ketoxime ester compounds represented by the following general formula (25).

[0155] [Chemical 14]

[0156] In equation (24), R24 has the same meaning as R22 in equation (22).

[0157] [Chemistry 15]

[0158] In formula (25), R23a represents a substituted phenyl, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 3 to 20 carbon atoms, a phenoxycarbonyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkoxyalkyl group having 3 to 8 carbon atoms, an aryl group having 7 to 20 carbon atoms, a heteroaryl 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.

[0159] R23b represents any substituent containing an aromatic ring or a heteroaromatic ring. Furthermore, R23a may form a ring together with R23b, and the linking group may be, for example, an alkyl group having 1 to 10 carbon atoms, a polyvinyl group (-(CH=CH)r-), a polyvinylethynyl group (-(C≡C)r-), or a group formed by combining the above (where r is an integer from 0 to 3).

[0160] R24a represents an alkyl group with 2 to 12 carbon atoms, an alkenyl group with 3 to 25 carbon atoms, a cycloalkaneyl group with 4 to 8 carbon atoms, a benzoyl group with 7 to 20 carbon atoms, a heteroaryl group with 3 to 20 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, an aryloxycarbonyl group with 7 to 20 carbon atoms, a heteroaryl group with 2 to 20 carbon atoms, or an alkylaminocarbonyl group with 2 to 20 carbon atoms. Preferably, R24 in formula (24) and R24a in the above general formula (25) are: an alkyl group with 2 to 12 carbon atoms, a heteroarylalkyl group with 1 to 20 carbon atoms, a cycloalkaneyl group with 3 to 8 carbon atoms, or an aryl group with 7 to 20 carbon atoms.

[0161] As R23a in formula (25), examples are preferably unsubstituted ethyl, propyl, butyl, or methoxycarbonyl-substituted ethyl or propyl. As R23b in formula (25), examples are preferably substituted carbazole or substituted phenyl thioether. Specifically, compounds as illustrated below can be cited as suitable ketooxime ester compounds for the present invention, but are not limited to any of these compounds.

[0162] [Chemistry 16]

[0163] [Chemical 17]

[0164] [Chemical 18]

[0165] Commercially available photopolymerization initiators for this type of ketoxime ester compound include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Qiangli Electronics Co., Ltd.

[0166] These oxime ester compounds and ketoxime ester compounds are known compounds, for example, one of the series of compounds described in Japanese Patent Application Publication No. 2000-80068 or Japanese Patent Application Publication No. 2006-36750. The above-mentioned photopolymerization initiator can be used alone or in combination of two or more.

[0167] In addition, examples include: benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and other benzoin alkyl ethers; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, milchnerone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; and benzophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, and 1-hydroxy-1-(p-decyl)acetophenone. Acetophenone derivatives such as dialkylphenyl ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl) ketone; 9-oxothiophene, 2-ethyl-9-oxothiophene, 2-isopropyl-9-oxothiophene, 2-chloro-9-oxothiophene, 2,4-dimethyl-9-oxothiophene, and 2,4-diethyl-9-oxothiophene. 9-Oxysulfur derivatives such as 2,4-diisopropyl9-oxosulfur; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; benzyl derivatives such as 9,10-dimethylbenzophenone; and anthrone derivatives such as benzoanthrone.

[0168] <Sensitizing Pigment> To improve sensitivity, a sensitizing pigment corresponding to the wavelength of the image exposure light source may be used in combination with a (F) photopolymerization initiator, as needed. Examples of such sensitizing pigments include: the pigments described in Japanese Patent Application Publication No. 4-221958 and Japanese Patent Application Publication No. 4-219756; heterocyclic coumarin pigments described in Japanese Patent Application Publication No. 3-239703 and Japanese Patent Application Publication No. 5-289335; 3-ketocoumarin compounds described in Japanese Patent Application Publication No. 3-239703 and Japanese Patent Application Publication No. 5-289335; pyrrole methylene pigments described in Japanese Patent Application Publication No. 6-19240; and Japanese Patent Application Publication No. 47-2528 and Japanese Patent Application Publication No. 54-155292. Pigments having a dialkylaminobenzene skeleton as described in the following publications: Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. 2-69, Japanese Patent Publication No. 57-168088, Japanese Patent Publication No. 5-107761, Japanese Patent Publication No. 5-210240, and Japanese Patent Publication No. 4-288818.

[0169] Among these sensitizing pigments, it is preferred to be an amino-containing sensitizing pigment, and more preferably a compound having both an amino group and a phenyl group within the same molecule, such as: 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone compounds; 2-(p-dimethylaminophenyl)benzo[4,5] ... Benzo[6,7]benzo[6,7]benzo[7]azole, 2,5-bis(p-diethylaminophenyl)1,3,4-benzo[6,7]azole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, and other compounds containing p-dialkylaminophenyl groups. 4,4'-Dialkylaminobenzophenone is particularly preferred. Sensitizing dyes can be used alone or in combination of two or more.

[0170] (F) The content ratio of the photopolymerization initiator is not particularly limited, but relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, even more preferably 4% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, and even more preferably 8% by mass or less. By setting it to the above-mentioned lower limit value or above, there is a tendency to increase sensitivity. Furthermore, by setting it to the above-mentioned upper limit value or below, there is a tendency to increase the adhesion stress with the substrate. The above-mentioned upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, further preferably 2 to 15% by mass, further preferably 3 to 10% by mass, and even more preferably 4 to 8% by mass.

[0171] When the photosensitive resin composition of the present invention contains an oxime ester compound as a (F) photopolymerization initiator, the content ratio of the oxime ester compound is not particularly limited. Relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and even more preferably 4% by mass or more. It is also preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, and even more preferably 8% by mass or less. By setting it to the lower limit or above, there is a tendency to improve sensitivity, and the fine line adhesion becomes better. Furthermore, by setting it to the upper limit or below, there is a tendency to increase the solubility of the unexposed portion in the developer. The upper and lower limits can be arbitrarily combined. The preferred concentration is 1–30% by mass, more preferably 1–20% by mass, further preferably 2–15% by mass, further preferably 3–10% by mass, and especially preferably 4–8% by mass.

[0172] Furthermore, when using a sensitizing pigment, the content of the sensitizing pigment in the total solids of the photosensitive resin composition is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.

[0173] <Surfactant> The photosensitive resin composition of the present invention may also contain a surfactant to adjust the coatability. Examples of surfactants include: BYK-330 (manufactured by BYK-Chemie, surface tension 24.4 mN / m), F-475 (manufactured by DIC, surface tension 25.4 mN / m), and F-554 (manufactured by DIC, surface tension 23.3 mN / m). Furthermore, one surfactant may be used, or two or more surfactants may be used in any combination and ratio.

[0174] When the photosensitive resin composition of the present invention contains a surfactant, the content ratio of the surfactant is not particularly limited. In the total solids content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more. It is also preferably 1.0% by mass or less, more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less. By setting it to the lower limit or above, the coating uniformity tends to improve, thereby improving the fine line adhesion. Furthermore, by setting it to the upper limit or below, the sensitivity tends to improve. The upper and lower limits can be arbitrarily combined. For example, it is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.7% by mass, further preferably 0.1 to 0.5% by mass, and even more preferably 0.15 to 0.3% by mass.

[0175] <Solvent> The photosensitive resin composition of the present invention is used, for example, in a state in which (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator, and various materials as needed, are dissolved or dispersed in an organic solvent. As an organic solvent, it is preferred to select an organic solvent with a boiling point (under a pressure of 1013.25 [hPa], the same applies to boiling point below) in the range of 100 to 300°C, and more preferably an organic solvent with a boiling point in the range of 120 to 280°C.

[0176] Examples of organic solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and other diol monoalkyl ethers;

[0177] Dialkyl ethers of glycols 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; Dialkyl ether acetates of glycols 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;

[0178] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as pentylenetetrazol, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl pentylenetetrazol, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentylenetetrazol, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentylenetetrazol; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentylenetetrazol, glycerol, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipeptene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl.

[0179] 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, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0180] Halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzo[a]nitrile. Examples of commercially available solvents include: mineral oil, Barsol #2, Apco #18 Solvent, Apco diluent, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (all trade names).

[0181] These organic solvents may be used alone or in combination of two or more. When forming pixels or black matrices of a color filter using photolithography, it is preferable to choose an organic solvent with a boiling point of 100 to 250°C, and more preferably an organic solvent with a boiling point of 120 to 230°C. In terms of good balance of coatability, surface tension, etc., and relatively high solubility of each component of the photosensitive resin composition, it is preferable to choose a glycol alkyl ether acetate as the organic solvent.

[0182] Diol alkyl ether acetates can be used alone or in combination with other organic solvents. Preferred other organic solvents for combination are monoalkyl glycol ethers, and propylene glycol monomethyl ether is preferred in terms of the solubility of the constituent components in the composition. From the viewpoint of the storage stability of the obtained photosensitive resin composition, the ratio of monoalkyl glycol ethers in the organic solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0183] Furthermore, an organic solvent with a boiling point of 200°C or higher (hereinafter sometimes referred to as a "high-boiling-point solvent") may also be used. By using a high-boiling-point solvent, the photosensitive resin composition is less likely to dry out, and the uniform dispersion of the pigment in the composition is prevented from being destroyed by rapid drying. That is, it prevents foreign matter defects caused by precipitation and curing of pigments, for example, at the tip of a slit nozzle. In terms of the higher effectiveness, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, triacetylglycerol, and 1,6-hexanediol diacetate are preferred as high-boiling-point solvents.

[0184] When the organic solvent contains a high-boiling-point solvent, the content of the high-boiling-point solvent in the organic solvent is preferably 0-50% by mass, more preferably 0.5-40% by mass, and even more preferably 1-30% by mass. By setting it to the lower limit or above, the tendency for foreign matter defects caused by pigment precipitation and curing at the tip of a slit nozzle, for example, can be suppressed. Furthermore, by setting it to the upper limit or below, the drying temperature of the composition slows down, which can suppress the tendency for problems such as poor yield in the reduced pressure drying process or pre-baking pore marks to occur in the color filter manufacturing process.

[0185] When the photosensitive resin composition of the present invention contains an organic solvent, the content ratio of the organic solvent is not particularly limited. From the viewpoint of ease of application and viscosity stability, it is preferred that the total solids content in the photosensitive resin composition is 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and especially preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it can be added in a manner where the total solids content in the photosensitive resin composition is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, further preferably 8 to 25% by mass, and especially preferably 10 to 20% by mass.

[0186] <Other formulations of the photosensitive resin composition> In addition to the above-mentioned components, the photosensitive resin composition of the present invention may also be appropriately formulated with, for example, thiols, additives, developer modifiers, ultraviolet absorbers, and antioxidants.

[0187] <Thiols> In order to achieve high sensitivity and improve adhesion to the substrate, the photosensitive resin composition of the present invention may also contain thiols. Examples of thiols include: hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene glycol dimercaptopropionate, butylene glycol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butylene glycol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyroxyloxy)butane (trade name: Karenz MT BD1, manufactured by Showa Denko), butylene glycol trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate) (trade name: Karenz MT). PE1 (manufactured by Showa Denko Co., Ltd.), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butylene glycol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.); these can be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1, more preferably Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1, and even more preferably Karenz MT PE1.

[0188] When the photosensitive resin composition of the present invention contains thiols, the content ratio of thiols relative to the total solids content of the photosensitive resin composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, and preferably 10% by mass or less, and even more preferably 5% by mass or less. By setting it to the lower limit or above, there is a tendency to suppress the decrease in sensitivity. Furthermore, by setting it to the upper limit or below, there is a tendency to easily achieve good storage stability. The upper and lower limits can be arbitrarily combined. For example, it is preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, and even more preferably 0.5 to 5% by mass.

[0189] <Additives> To improve adhesion to the substrate, additives may also be included. Examples include silane coupling agents and titanium coupling agents. Silane coupling agents are particularly preferred. Examples of silane coupling agents include: KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicones), Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning). One type of silane coupling agent may be used, or two or more may be used in combination. Furthermore, the photosensitive resin composition of the present invention may also contain additives other than silane coupling agents, such as phosphoric acid additives and other additives.

[0190] As a phosphoric acid additive, it is preferably a (meth)acryloxyphosphate. Among them, it is preferably represented by the following general formulas (g1), (g2), and (g3).

[0191] [Chemistry 19]

[0192] In formulas (g1), (g2), and (g3), R51 independently represents a hydrogen atom or a methyl group, l and l' are independently integers from 1 to 10, and m is independently 1, 2, or 3. Other additives include, for example, TEGO*Add Bond LTH (manufactured by Evonik). These phosphate-containing compounds or other binders can be used alone or in combination of two or more.

[0193] When the photosensitive resin composition of the present invention contains additives, the content ratio of the additives is not particularly limited. In the total solids content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, further preferably 0.50% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less. By setting it to the lower limit or above, there is a tendency to improve adhesion. Furthermore, by setting it to the upper limit or below, there is a tendency to improve developability. The upper and lower limits can be arbitrarily combined. For example, it is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, further preferably 0.10 to 2.0% by mass, and even more preferably 0.50 to 1.5% by mass.

[0194] <Properties of the Photosensitive Resin Composition> The photosensitive resin composition of the present invention is preferably used for forming a black matrix. From this point of view, it is preferable to present a black color. Furthermore, the optical density (OD value) per 1.0 μm of film thickness of the cured coating is preferably 4.0 or higher. More preferably 4.1 or higher, even more preferably 4.2 or higher, and preferably 6.0 or lower. By setting it to the above lower limit value or higher, there is a tendency to ensure sufficient light-blocking properties. For example, it is preferably 4.0 to 6.0, more preferably 4.1 to 6.0, and even more preferably 4.2 to 6.0. The optical density refers to the transmittance of the light-receiving portion as expressed by the ISO visual density in the ISO 5-3 standard. Generally, as a light source, an A-type light source as specified by the CIE (International Commission on Illumination) is used. As an instrument that can be used to measure the concentration transmitted through optical light, an example is the X-Rite 361T(V) from Sakata Inx Engineering.

[0195] <Method for Manufacturing Pigment Dispersion> The pigment dispersion of the present invention is manufactured by conventional methods. The (A) pigment is preferably pre-dispersed using, for example, a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, or homogenizer. This dispersion treatment micronizes the (A) pigment, thereby improving the coating properties of the photosensitive resin composition. When using a black pigment as the (A) pigment, it helps to improve the light-blocking ability.

[0196] Dispersion treatment is generally preferably carried out in a system comprising (A) pigment, (B) dispersant, (C) sulfonic acid compound, solvent, and (D) alkali-soluble resin, if necessary (hereinafter, the mixture supplied for dispersion treatment and the pigment dispersion obtained in dispersion treatment are sometimes referred to as "ink"). If a polymeric dispersant is used as the dispersant, the viscosity increase of the obtained ink over time is suppressed (excellent dispersion stability), which is therefore preferable.

[0197] When using a sand mill to disperse pigment (A), it is preferable to use glass beads, zircon particles, or zircon oxide particles with a diameter of approximately 0.1 to 8 mm. The temperature conditions for dispersion treatment are preferably 0°C to 100°C, and more preferably room temperature (25°C) to 80°C. Regarding the dispersion time, the exact time varies depending on the liquid composition and the size of the dispersion treatment device, and should be adjusted accordingly. The dispersion target is to control the gloss of the ink in such a way that the 20-degree specular gloss of the photosensitive resin composition (JIS Z8741) is in the range of 100 to 200. If the 20-degree specular gloss of the photosensitive resin composition is 100 or higher, the dispersion treatment becomes sufficient, the residue of coarse pigment (colorant) particles can be suppressed, and sufficient developability, adhesion, and resolution can be easily obtained. Furthermore, if the 20-degree specular gloss value is 200 or lower, the pigment will not be excessively broken down, the generation of a large number of ultrafine particles can be suppressed, and the dispersion stability is not easily damaged.

[0198] <Method for Manufacturing Photosensitive Resin Composition> The photosensitive resin composition of the present invention is manufactured by a conventional method. For example, the ink obtained by the above dispersion treatment can be mixed with other components contained in the photosensitive resin composition to form a homogeneous solution. In the manufacturing steps of the photosensitive resin composition, fine dust is often mixed into the liquid; therefore, it is preferable to filter the obtained photosensitive resin composition using a filter or the like.

[0199] [Curved Material] The cured material of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The cured material obtained by curing the photosensitive resin composition of the present invention can be preferably used as a component constituting a color filter, such as a pixel, black matrix, or colored isolation element.

[0200] [Black Matrix] The black matrix of the present invention includes the hardened material of the present invention.

[0201] (1) The support used to form the black matrix is ​​not particularly limited in material, as long as the strength is appropriate. A transparent substrate is preferred. Examples of materials for transparent substrates include: polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polyurethane; thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin; and various types of glass. From the point of view of heat resistance, glass and heat-resistant resins are preferred. Transparent electrodes such as ITO (Indium Tin Oxides) and IZO (Indium Zinc Oxide) can also be formed on the surface of the substrate. In addition to transparent substrates, transparent electrodes can also be formed on TFT (Thin-Film Transistor) arrays.

[0202] To improve surface properties such as adhesion, the support may be subjected to various resin film formation treatments, such as corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, or urethane resin, as needed. The thickness of the support is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. When performing various resin film formation treatments, the film thickness is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0203] (2) When the black matrix is ​​formed by the photosensitive resin composition of the present invention, the photosensitive resin composition can be coated on a transparent substrate and dried, and then the image is exposed, developed, and thermo-cured or photo-cured as needed through a photomask disposed on the transparent substrate on which the photosensitive resin composition is coated and dried, thereby forming the black matrix.

[0204] (3) Formation of the black matrix (3-1) Coating of the photosensitive resin composition The photosensitive resin composition used for coating the black matrix onto the transparent substrate can be performed by, for example, spin coating, wire rod coating, flow coating, die coating, roller coating, or spray coating. Among these, die coating is preferred from the viewpoints of significantly reducing the amount of coating liquid used, eliminating the influence of fog and other effects that occur when using spin coating, and suppressing the generation of foreign matter.

[0205] The thickness of the coating, measured as the film thickness 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 it below the above upper limit, pattern development tends to be easier, and gap adjustment in the liquid crystal unitization step also tends to be easier. By setting it above the above lower limit, the desired color representation tends to be easier.

[0206] (3-2) Drying of the Coating Film The drying of the coating film after the photosensitive resin composition is applied to the substrate is preferably carried out by vacuum drying using a vacuum drying apparatus, or by heating drying using a heated plate, an IR (Infrared Radiation) oven, or a convection oven. When using heating drying with a heated plate, the substrate can also be supported from the back using pins. The heating drying conditions can be appropriately selected according to the type of organic solvent and the performance of the dryer used. Preferably, it is at a temperature of 40–200°C for 15 seconds to 5 minutes, more preferably at a temperature of 50–130°C for 30 seconds to 3 minutes.

[0207] The higher the drying temperature, the better the adhesion of the coating to the transparent substrate. If it is below the above-mentioned upper limit, sufficient adhesion of the coating to the transparent substrate can be ensured, and the tendency of alkali-soluble resin decomposition, inducing thermal polymerization and resulting in poor development can be suppressed. Furthermore, by setting the drying temperature below the above-mentioned upper limit, the film thickness shrinks uniformly, and the tendency of unevenness on the coating surface can be suppressed.

[0208] (3-3) Image exposure can be performed by overlaying a negative mask pattern on a coating of a photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible light range through the mask pattern. At this time, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer can be formed on the photopolymerizable coating before exposure, as needed. There are no particular limitations on the light source used for the above image exposure. Examples of light sources include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and other arc light sources. When used after irradiating light of a specific wavelength, an optical filter can also be used.

[0209] (3-4) The black matrix of the present invention can be produced by exposing a coating film formed of a photosensitive resin composition to an image using the above-mentioned light source, and then developing it on a substrate using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. The aqueous solution may further contain an organic solvent, a buffer, a bonding agent, a dye, and a pigment.

[0210] Examples of basic compounds include: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic basic compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono-, or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethylenediimide, ethylenediimide, tetramethylammonium hydroxide (TMAH), and choline. One of these basic compounds may be used alone, or two or more may be used in combination.

[0211] Examples of surfactants include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0212] Examples of organic solvents include: isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used alone or in combination with aqueous solutions. There are no particular limitations on the developing conditions. The developing temperature is preferably 10–50°C, more preferably 15–45°C, and even more preferably 20–40°C. Developing methods include, for example, immersion developing, spray developing, brush developing, and ultrasonic developing.

[0213] (3-5) Thermal curing treatment: The substrate after development is subjected to thermal curing treatment or photocuring treatment, preferably thermal curing treatment. The temperature is preferably 100-280°C, more preferably 150-250°C. The time is preferably 5-60 minutes. The height of the black matrix formed in the above manner is preferably 0.5-5 μm, more preferably 0.8-4 μm.

[0214] [Forming of Color Filters and Other Procedures] On a transparent substrate with a black matrix, a photosensitive resin composition containing one of the colors red, green, and blue is coated and dried using the same process as described in (3-1) to (3-5) above. A photomask is then superimposed on the coating, and the image is exposed, developed, and, if necessary, heat-cured or photo-cured to form a pixel image, thereby creating a color layer. This operation is performed separately for the photosensitive resin compositions of the three colors red, green, and blue (in any order) to form a color filter.

[0215] [Colored Isolator] The photosensitive resin composition of the present invention, in addition to the black matrix, can also be used as a photosensitive resin composition for a colored isolator. When the isolator is used in a TFT-type LCD (Liquid Crystal Display), there is a possibility that the TFT, as a switching element, may malfunction due to light incident on it. The colored isolator is used to prevent this malfunction. For example, Japanese Patent Application Publication No. 8-234212 describes an isolator with light-shielding properties. The colored isolator can be formed using the same method as the black matrix described above, except that a mask for a colored isolator is used.

[0216] (3-6) Formation of Transparent Electrodes In this state, transparent electrodes such as ITO are formed on the image, and the color filter is used as a component in color displays, liquid crystal display devices, etc. To improve the surface smoothness and durability of the color filter, a top coating such as polyamide or polyimide can also be provided on the image as needed. For example, in applications using planar alignment type driving mode (IPS mode), transparent electrodes may not be formed.

[0217] [Image Display Device] The image display device of the present invention has the hardened version of the present invention. The image display device is any device that displays images or videos and is not particularly limited thereto. Examples include liquid crystal display devices or organic EL (Electroluminescence) displays.

[0218] [Liquid Crystal Display Device] The liquid crystal display device of the present invention has the hardened material of the present invention, especially the black matrix, and the formation order or formation position of the color pixels or the black matrix is ​​not particularly limited.

[0219] A liquid crystal display device can be manufactured as follows: an alignment film is formed on a color filter, spacers are distributed on the alignment film, and the film is bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell and wired to a counter electrode. The alignment film is preferably a resin film such as polyimide. The alignment film can be formed by gravure printing and / or flexible printing, and the thickness of the alignment film can be tens of nm. Alternatively, after hardening the alignment film by thermal baking, a surface treatment can be performed by ultraviolet irradiation or by using a rubbing cloth to obtain a surface state in which the liquid crystal slope can be adjusted.

[0220] As the isolation element, an isolation element with a size corresponding to the gap between the opposing substrates is preferably used, and is preferably 2 to 8 μm. Alternatively, a photosensitive isolation element (PS) with a transparent resin film can be formed on the color filter substrate by photolithography, and this photosensitive isolation element can be used instead of the isolation element. As the opposing substrate, an array substrate can be used, and a TFT (thin-film transistor) substrate is particularly preferred.

[0221] The bonding gap between the liquid crystal display device and the opposing substrate varies depending on the application of the liquid crystal display device and can be 2 to 8 μm. After bonding with the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV (ultraviolet) irradiation and / or heating to seal the periphery of the liquid crystal cell. After the liquid crystal cell with the periphery sealed is cut into panel units, the vacuum chamber is depressurized, the liquid crystal injection port is immersed in liquid crystal, and the chamber is depressurized to inject liquid crystal into the liquid crystal cell. The depressurization degree in the liquid crystal cell is preferably 1×10-2 to 1×10-7 Pa, more preferably 1×10-3 to 1×10-6 Pa. Furthermore, it is preferable to heat the liquid crystal cell during depressurization, the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. The heating during depressurization can be maintained for 10 to 60 minutes, after which the cell is immersed in liquid crystal. After liquid crystal is injected, the liquid crystal injection port is sealed by UV-curing resin, thereby completing the liquid crystal display device (panel).

[0222] There are no particular limitations on the type of liquid crystal. For example, it can be a liquid crystal known from the prior art, such as aromatic liquid crystals, aliphatic liquid crystals, or polycyclic liquid crystals, such as liquid-tropic liquid crystals or thermal liquid crystals. As a thermal liquid crystal, it can be any of the following: nematic liquid crystals, smectic liquid crystals, or cholesteric liquid crystals.

[0223] [Organic EL Display] The organic EL display of the present invention is manufactured using the color filter of the present invention.

[0224] When using the color filter of the present invention to manufacture an organic EL display, as shown in FIG1, firstly, a color filter is formed on a transparent support substrate 10 by forming a pattern (i.e., pixels 20 and resin black matrices (not shown)) formed by a photosensitive resin composition. An organic light emitter 500 is then deposited on the color filter via an organic protective layer 30 and an inorganic oxide film 40, thereby manufacturing an organic EL element 100. Furthermore, at least one of the pixels 20 and the resin black matrix is ​​made using the photosensitive resin composition of the present invention. Examples of methods for depositing the organic light emitter 500 include: sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter; or attaching an organic light emitter 500 formed on another substrate to the inorganic oxide film 40. An organic EL element 100 made in the manner described above can be used to make an organic EL display using, for example, the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, written by Shizushi Tokito, Chinatsuya Adachi, and Hideyuki Murata).

[0225] The color filter of this invention can be applied to either passively driven or actively driven organic EL displays. [Example]

[0226] Examples of synthesis, embodiments and comparative examples are given to illustrate the present invention in more detail, but the present invention is not limited to the following embodiments as long as it does not depart from its spirit.

[0227] <Synthesis Example: Synthesis of Alkali-Soluble Resin>

[0228] [Chemical 20]

[0229] 240 parts by mass of the epoxy compound with the above structure (epoxy equivalent 264), 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of p-methoxyphenol were added to a flask equipped with a thermometer, a stirrer, and a condenser. The mixture was stirred and reacted at 90°C for 12 hours until the acid value became below 5 mgKOH / g. Subsequently, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), and 51.6 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction solution obtained by the above reaction in a flask equipped with a thermometer, stirrer, and condenser. While stirring, the temperature was slowly raised to 105°C to allow the reaction to proceed, resulting in an alkali-soluble resin with a solid content acid value of 112 mgKOH / g and a weight average molecular weight (Mw) of 2500 converted from polystyrene by GPC.

[0230] The components of the pigment dispersion and photosensitive resin composition used in the following examples and comparative examples are as follows.

[0231] <Pigment-1> R1060: "RAVEN1060" (carbon black) manufactured by BIRLA CARBON.

[0232] <Dispersant-1> BYK167: BYK-Chemie manufactures "DISPERBYK-167" (carbamate-based polymeric dispersant).

[0233] <Sulfonic Acid Compounds A-D, Compound E> S12000-S: Lubrizol Corporation manufactures "S12000-S" (phthalocyanine copper sulfonic acid derivative). S12000-S, whose conductivity has been altered by changing the amount of acid added during manufacturing and the washing process, is used for sulfonic acid compounds A-D. Compound E uses phthalocyanine copper pigment. Sulfonic acid compound A: Conductivity 2080 μS / cm, Acid value 80 mgKOH / g; Sulfonic acid compound B: Conductivity 5100 μS / cm, Acid value 81 mgKOH / g; Sulfonic acid compound C: Conductivity 9012 μS / cm, Acid value 83 mgKOH / g; Sulfonic acid compound D: Conductivity 1420 μS / cm, Acid value 40 mgKOH / g; Compound E: CI Pigment Blue 15:6 (Conductivity 0 μS / cm, Acid value 0 mgKOH / g).

[0234] <Alkali-soluble resin-1> Alkali-soluble resin-1: The resin described in the synthesis example

[0235] <Photopolymerizable Compound-1> DPHA: "KAYARAD DPHA" (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.

[0236] <Photopolymerization Initiator-1> TR-PBG-304: "TR-PBG-304" (an oxime ester compound with a carbazole skeleton) manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.

[0237] <Additive-1> X-12-1048: Shin-Etsu Chemical Co., Ltd. manufactures "X-12-1048" (polyfunctional acrylic silane).

[0238] <Surfactant-1> F-554: MEGAFAC F554 (fluorinated surfactant) manufactured by DIC Corporation

[0239] <Solvent> PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0240] <Preparation of Dispersions 1-7> Pigment-1, dispersant-1, sulfonic acid compounds A-D, compound E, and solvent as described in Table 1 were mixed in the mass ratios shown in Table 1 to obtain a mixture. Furthermore, the solvent ratios in Table 1 also include the amounts of solvent derived from the dispersant and the compounds. The mixture was dispersed for 6 hours at 25-45°C using a paint shaker. Zirconia particles of 0.5 mm were used as particles, and 2.5 times the mass of the dispersion was added. After dispersion, the particles were separated from the dispersion using a filter to prepare dispersions 1-7. These pigment dispersions (dispersions 1-7) showed good dispersibility without thickening.

[0241] [Table 1] Detailed ingredients mass ratio Dispersion 1 2 3 4 5 6 7 Pigment-1 28.7 28.7 26.9 27.6 28.7 28.7 28.7 Dispersant-1 5.7 5.7 5.4 6.9 5.7 5.7 5.7 Compound A containing sulfonic acid group 0.6 2.7 0.6 Compound B containing sulfonic acid group 0.6 Compound C containing sulfonic acid group 0.6 Compound D containing sulfonic acid group 0.6 Compound E 0.6 PGMEA 65.0 65.0 65.0 65.0 65.0 65.0 65.0 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[0242] <Preparation of Photosensitive Resin Compositions> [Examples 1-4 and Comparative Examples 1-3] Using the dispersions 1-7 prepared above, each component was added in such a way that the solid content ratio of each component in the total solid content of the photosensitive resin composition was the mixing ratio shown in Table 2. Propylene glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate (MBA), and diethylene glycol monoethyl ether acetate (EDGAC) were added in such a way that the content ratio of the total solid content of the photosensitive resin composition was 14% by mass, and the ratio in the solvent was 68 / 30 / 2% by mass for PGMEA / MBA / EDGAC. The mixture was stirred until dissolved to prepare a photosensitive resin composition. The obtained photosensitive resin compositions were evaluated using the methods described below.

[0243] [Table 2] Types of ingredients Detailed ingredients Solid content percentage [mass %] Example Comparative example 1 2 3 4 1 2 3 Pigment dispersion Dispersion 1 61.0 Dispersion 2 61.0 Dispersion 3 65.0 Dispersion 4 63.5 Dispersion 5 61.0 Dispersion 6 61.0 Dispersion 7 61.0 Alkali-soluble resins Alkali-soluble resin-1 25.3 25.3 22.2 23.3 25.3 25.3 25.3 Photopolymer compounds Photopolymerizable compound-1 7.1 7.1 6.2 6.6 7.1 7.1 7.1 Photopolymerization initiator Photopolymerization Initiator-1 6.0 6.0 6.0 6.0 6.0 6.0 6.0 surfactants Surfactant-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 additive Additive-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Evaluation Project Dissolution time (seconds) 29.0 29.0 26.5 31.0 25.0 34.9 44.7 Fine-line adhesion (μm) 7.0 7.0 8.0 8.0 10.0 10.0 15.0 linearity A A A A B C C

[0244] (Evaluation of the photosensitive resin composition) <Determination of dissolution time> The photosensitive resin composition was coated onto a glass substrate with a thickness of 1.2 μm after heat curing using a spin coater. After drying under reduced pressure of 100 Pa for 60 seconds, it was dried at 100°C for 120 seconds using a heated plate. Using a photomask with a linewidth of 1 μm to 20 μm on a 1 μm scale, the obtained coating was exposed to ultraviolet light at a wavelength of 365 nm and an intensity of 60 mW / cm², with an exposure dose of 40 mJ / cm². Subsequently, the coating was developed using a developer containing 0.04% by mass of KOH (potassium hydroxide) aqueous solution at 23°C under a water pressure of 0.05 MPa. Development was then stopped using pure water, and the coating was rinsed with a water spray. The time during which patterning was visually visible during the development was measured as the dissolution time.

[0245] <Evaluation of Fine Line Adhesion> A photosensitive resin composition was coated onto a glass substrate using a spin coater to achieve a film thickness of 1.2 μm after heat curing. The coating was dried under reduced pressure of 100 Pa for 60 seconds, followed by drying at 100°C for 120 seconds using a heated plate. Using a photomask with a linewidth aperture of 1 μm to 20 μm (1 μm scale), the obtained coating was exposed to ultraviolet light at a wavelength of 365 nm and an intensity of 60 mW / cm², with an exposure dose of 40 mJ / cm². Subsequently, a developing solution containing 0.04% by mass KOH (potassium hydroxide) aqueous solution was used for shower development at 23°C for twice the dissolution time at a water pressure of 0.05 MPa. Development was then stopped using pure water, followed by rinsing with a water spray. The substrate was then heat-cured at 230°C for 25 minutes (and subsequently baked) to produce a substrate for evaluating fine line adhesion. The linear patterns of the obtained substrate were observed using an optical microscope (Nikon Eclipse L200ND), and the size of the photomask opening of the smallest undamaged and remaining pattern was measured as the minimum tightness (fine line tightness).

[0246] <Straightness> The substrate is fabricated using the same method as the substrate used for evaluating the adhesion of fine lines. The straightness of the pattern corresponding to the 6 μm opening of the photomask is measured using an optical microscope. A: No defects are found. B: 2 to 3 defects are found, but they do not pose a problem for manufacturing color filters. C: Numerous defects are found, making it unsuitable for manufacturing color filters.

[0247] As shown in Examples 1, 2, and Comparative Example 1, as long as the conductivity of the (C) sulfonic acid compound is 9000 μS / cm or less and the acid value is 40 mgKOH / g or more, the developing solubility and fine line adhesion are excellent. On the other hand, it is believed that if the conductivity of the (C) sulfonic acid compound exceeds 9000 μS / cm, i.e., the conductivity becomes high, the amount of free acid increases due to poor adsorption of the pigment in the (C) sulfonic acid compound, which is believed to accelerate the dissolution time, strengthen the undercut, and therefore worsen the fine line adhesion. According to Examples 1, 3, and Comparative Example 1, as long as the conductivity of the (C) sulfonic acid compound is 9000 μS / cm or less, even if the amount of the (C) sulfonic acid compound relative to the amount of pigment is increased from 2% to 10%, the fine line adhesion will not worsen, and the dissolution rate will not change significantly. According to Examples 1, 4 and Comparative Example 1, as long as the conductivity of the (C) sulfonic acid compound is below 9000 μS / cm, even if the amount of dispersant relative to the amount of pigment is increased from 20% to 25%, the fine line adhesion will not deteriorate and the dissolution rate will not change significantly.

[0248] As shown in Example 1 and Comparative Example 2, if the conductivity of the sulfonic acid compound (C) is less than 2000 μS / cm, the acid value around the pigment decreases significantly, resulting in a longer dissolution time and poorer thread adhesion. It is also shown that the straightness deteriorates, making it difficult to produce fine threads. As shown in Example 1, Comparative Example 2, and Comparative Example 3, if the conductivity of the sulfonic acid compound (C) falls below 2000 μS / cm and the acid value falls below 40 mgKOH / g, the pigment adsorption capacity is lost, resulting in poor stability of the dispersion, further increasing the dissolution time, and consequently worsening the thread adhesion and straightness. The results above show that by making the conductivity of (C) sulfonic acid compound above 2000 μS / cm and below 9000 μS / cm, and the acid value above 40 mgKOH / g, the influence of free acid can be minimized, thereby improving the tightness and straightness of the fine line, and also reducing the variation in dissolution time. [Simplified Explanation of the Diagram]

[0015] FIG1 is a schematic cross-sectional view of an example of an organic EL element having the color filter of the present invention.

Claims

1. A pigment dispersion comprising (A) a pigment, (B) a dispersant and (C) a sulfonic acid compound, wherein the (A) pigment contains carbon black, the (C) sulfonic acid compound contains a copper phthalocyanine sulfonic acid derivative, the (C) sulfonic acid compound has a conductivity of 2000 μS / cm or more and 7000 μS / cm or less, and the (C) sulfonic acid compound has an acid value of 60 mgKOH / g or more and 150 mgKOH / g or less.

2. The pigment dispersion of claim 1, wherein the ratio of the above-mentioned (A) pigment to the above-mentioned (C) sulfonic acid compound, based on mass ((A) pigment / (C) sulfonic acid compound) is 10 or more.

3. The pigment dispersion of claim 1, wherein the ratio of the above-mentioned (A) pigment to the above-mentioned (C) sulfonic acid compound, based on a mass basis ((A) pigment / (C) sulfonic acid compound) is 25 or more.

4. The pigment dispersion of any one of claims 1 to 3, wherein the content ratio of the above-mentioned (A) pigment to the above-mentioned (B) dispersant on a mass basis ((A) pigment / (B) dispersant) is 4 or more.

5. The pigment dispersion of any one of claims 1 to 3, wherein the conductivity of the sulfonic acid compound (C) is 2080 μS / cm or more and 5100 μS / cm or less, and the acid value of the sulfonic acid compound (C) is 80 mgKOH / g or more and 150 mgKOH / g or less.

6. A photosensitive resin composition comprising (A) a pigment, (B) a dispersant, (C) a sulfonic acid-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator, wherein the (A) pigment comprises carbon black, the (C) sulfonic acid-containing compound comprises a copper phthalocyanine sulfonic acid derivative, the (C) sulfonic acid-containing compound has a conductivity of 2000 μS / cm or more and 7000 μS / cm or less, and the (C) sulfonic acid-containing compound has an acid value of 60 mgKOH / g or more and 150 mgKOH / g or less.

7. The photosensitive resin composition of claim 6, wherein the content of the pigment (A) is 30% by mass or more relative to the total solids content of the photosensitive resin composition.

8. The photosensitive resin composition of claim 6, wherein the conductivity of the sulfonic acid compound (C) is 2080 μS / cm or more and 5100 μS / cm or less, and the acid value of the sulfonic acid compound (C) is 80 mgKOH / g or more and 150 mgKOH / g or less.

9. A hardener formed by hardening a photosensitive resin composition as claimed in any one of claims 6 to 8.

10. A black matrix comprising the hardened material as claimed in claim 9.

11. An image display device having a hardened material as claimed in claim 9.

Images