WO2023204314A1

WO2023204314A1 - Pigment dispersion, photosensitive resin composition, cured product, black matrix, and image display device

Info

Publication number: WO2023204314A1
Application number: PCT/JP2023/016006
Authority: WO
Inventors: 宏明石井; 謙一入木; 翔藤本
Original assignee: 三菱ケミカル株式会社
Priority date: 2022-04-22
Filing date: 2023-04-21
Publication date: 2023-10-26
Also published as: TW202346487A

Abstract

Provided is a pigment dispersion that has excellent viscosity stability and yields a photosensitive resin composition in which the generation of pigment-derived foreign substances is suppressed. This pigment dispersion contains (A) a pigment, (B) a dispersant, an organic solvent and water, wherein the pigment (A) contains carbon black and has a moisture content of 0.15-0.9 mass%.

Description

Pigment dispersion, photosensitive resin composition, cured product, black matrix, and image display device

The present invention relates to a pigment dispersion, a photosensitive resin composition, a cured product, a black matrix, and an image display device.
This application claims priority based on Japanese Patent Application No. 2022-070967 filed with the Japan Patent Office on April 22, 2022, the contents of which are incorporated herein.

Color filters usually form a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially form pixels of three or more different colors, such as red, green, and blue, in a grid pattern or stripes. It is formed in a pattern such as a shape or a mosaic shape. The pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 μm.

A photolithography method using a photosensitive resin composition is currently known as a typical manufacturing method for color filters. In the photolithography method, for example, a photosensitive resin composition containing an alkali-soluble resin is applied onto a transparent substrate, dried to form a photosensitive resin film, the photosensitive resin film is exposed in a predetermined pattern, and then developed with an alkali. After developing with a liquid, a pattern is formed by curing it by high-temperature treatment at 200° C. or higher.
The photosensitive resin composition contains a coloring material when used for forming pixels of color filters, black matrices, etc. As the coloring material, pigments and dyes such as carbon black are used (Patent Document 1).

Japanese Patent Application Publication No. 2012-68613

In the production of color filters, the application of the photosensitive resin composition may be repeated using the same application device. According to studies by the present inventors, in the case of a photosensitive resin composition containing a pigment, foreign matter including aggregates of the pigment may be generated on the nozzle surface of the coating device during repeated coating. Such foreign matter may peel off from the nozzle and adhere to the photosensitive resin film or pattern, causing defects, which may adversely affect resolution and the like.

Therefore, the present invention provides a pigment dispersion that provides a photosensitive resin composition with excellent viscosity stability and suppressed generation of pigment-derived foreign substances, and a photosensitive resin composition with excellent viscosity stability and suppressed generation of pigment-derived foreign substances. The present invention aims to provide a synthetic resin composition, a cured product using the same, a black matrix, and an image display device.

As a result of intensive studies to solve the above problem, the present inventors found that the above problem could be solved by preparing the pigment in advance as a pigment dispersion containing a specific amount of water. That is, the gist of the present invention is as follows.

[1] A pigment dispersion containing (A) a pigment, (B) a dispersant, an organic solvent, and water,
The pigment (A) contains carbon black,
A pigment dispersion liquid having a moisture content of 0.15% by mass or more and 0.9% by mass or less.
[2] The pigment dispersion according to [1], which has a moisture content of 0.2% by mass or more and 0.7% by mass or less.
[3] The pigment dispersion according to [1] or [2], wherein the content ratio of the pigment (A) to the total solid content of the pigment dispersion is 60% by mass or more.
[4] Any of [1] to [3], wherein the content ratio of the (A) pigment and the (B) dispersant on a mass basis ((A) pigment/(B) dispersant) is 4 or more. Pigment dispersion liquid described in Crab.
[5] The pigment dispersion according to any one of [1] to [4], further containing (C) a dispersion aid.
[6] The pigment according to [5], wherein the content ratio ((A) pigment/(C) dispersion aid) of the (A) pigment and the (C) dispersion aid on a mass basis is 10 or more. dispersion liquid.
[7] A photosensitive resin composition containing the pigment dispersion according to any one of [1] to [6], (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator. thing.
[8] The photosensitive resin composition according to [7], wherein the content of the pigment (A) is 30% by mass or more based on the total solid content of the photosensitive resin composition.
[9] A cured product obtained by curing the photosensitive resin composition according to [7] or [8].
[10] A black matrix consisting of the cured product according to [9].
[11] An image display device comprising the cured product according to [9].

According to the present invention, a pigment dispersion can be obtained that provides a photosensitive resin composition that has excellent viscosity stability and suppresses the generation of pigment-derived foreign substances, and a pigment dispersion that has excellent viscosity stability and suppresses the generation of pigment-derived foreign substances. A photosensitive resin composition, a cured product using the same, a black matrix, and an image display device can be provided.

1 is a schematic cross-sectional view showing an example of an organic EL element in the present invention. 1 is a photograph showing the results of a peel test for the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2.

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 the scope of the gist.
In the present invention, "(meth)acrylic" means "acrylic and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".
In the present invention, "total solid content" means all components other than the organic solvent and water contained in the pigment dispersion or the photosensitive resin composition, and the components other than the organic solvent and water are liquid at room temperature. However, those components are not included in organic solvents and water, but are included in total solids.

In the present invention, the "moisture content" is calculated by the Karl Fischer measurement method described in JIS K0113 (2005). For the measurement, various moisture meters can be used, such as MKA-610 manufactured by Kyoto Electronics Industry Co., Ltd.
In the present invention, the "average particle size" of the pigment (A) is determined by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average thereof is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is determined by approximating it to a rectangular parallelepiped of the determined particle size, and the volume average particle size is determined and used as the average particle size. Note that the same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
In the present invention, the term "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, the "amine value" refers to the amine value in terms of effective solid content, unless otherwise specified, and is a value expressed by the amount of base and the mass of KOH equivalent to 1 g of solid content of the dispersant. The measurement method will be described later.

[Pigment dispersion]
The pigment dispersion of the present invention contains (A) a pigment, (B) a dispersant, an organic solvent, and water.

The moisture content of the pigment dispersion of the present invention is 0.15% by mass or more and 0.9% by mass or less based on the total mass of the pigment dispersion. When the water content of the pigment dispersion is 0.9% by mass or less, the viscosity stability is excellent, and thickening of the pigment dispersion and the accompanying decrease in filterability can be suppressed. When the moisture content is 0.15% by mass or more, it is possible to suppress the generation of pigment-derived foreign substances when forming a pattern using a photosensitive resin composition containing a pigment dispersion.
The water content of the pigment dispersion is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, further preferably 0.2% by mass or more, and more preferably 0.3% by mass or more.
The above upper and lower limits can be arbitrarily combined. For example, it may be 0.2% by mass or more and 0.7% by mass or less, and may be 0.3% by mass or more and 0.5% by mass or less.

<(A) Pigment>
(A) The pigment contains carbon black.
Containing carbon black tends to improve light shielding properties. On the other hand, foreign matter containing carbon black has a high light shielding rate and tends to have a negative effect on pattern resolution, for example. Therefore, the usefulness of the present invention is high when the pigment (A) contains carbon black.

Examples of carbon black include the following.
Made by Mitsubishi Chemical: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350 , #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B.
Manufactured by Degussa: Printex (registered trademark. The same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printe x85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialB rack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160 , Color Black S170.
Manufactured by Cabot: Monarch (registered trademark) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch h1400, Monarch4630, REGAL (registered trademark. The same applies hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8.
Made by Birler: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN85 0, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

Carbon black coated with resin may be used. Use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity. As the resin-coated carbon black, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.

It is preferable that the total content of Na and Ca be 100 ppm or less in the carbon black to be subjected to the resin coating treatment. Carbon black usually contains Na, Ca, K, Mg, Al, and Fe mixed in from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and reactor materials during manufacturing. The ash content is on the order of percent. Among these, Na and Ca are generally contained in amounts of several hundred ppm or more each, but by reducing their content, it is possible to suppress penetration into transparent electrodes (ITO) and other electrodes, and to This tends to prevent short circuits.

A method for reducing the content of ash containing Na and Ca is to carefully select materials with as low a content as possible as raw material oil, fuel oil (or gas), and reaction termination water when producing carbon black. This can be achieved by minimizing the amount of alkaline substances added to adjust the structure. Another method includes a method in which carbon black produced from a furnace is washed with water, hydrochloric acid, etc. to dissolve and remove Na and Ca.

Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, and a poorly soluble solvent is added to the water, the carbon black migrates to the solvent side and completely separates from the water. At the same time, most of the Na and Ca present in the carbon black are dissolved and removed by water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use only the carbon black manufacturing process with carefully selected raw materials or the water or acid dissolution method alone, but it is possible to further reduce the total amount of Na and Ca by using both methods together. The total amount of Na and Ca can be easily reduced to 100 ppm or less.

The resin-coated carbon black is preferably so-called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomilate diameter) in water becomes small, it is possible to coat even minute units, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less. Moreover, it is preferable that the amount of dibutyl phthalate (DBP) absorbed is 140 mL/100 g or less. When the average particle diameter and DBP absorption amount are within the above ranges, a coating film with good light-shielding properties tends to be obtained.

The method for preparing resin-coated carbon black is not particularly limited. For example, after adjusting the blending amounts of carbon black and resin as appropriate,
1. After mixing and stirring a resin solution in which a resin and a solvent such as cyclohexanone, toluene, or xylene are mixed and dissolved by heating, and a suspension in which carbon black and water are mixed to separate the carbon black and water, A method in which a composition obtained by removing water and heating and kneading is formed into a sheet shape, pulverized, and then dried;
2. A method of mixing and stirring a resin solution and a suspension prepared in the same manner as described above to granulate carbon black and resin, and then separating and heating the resulting granules to remove the remaining solvent and water;
3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and a resin is added to this. How to dry blend;
4. A suspension is prepared by stirring the reactive group-containing monomer component constituting the resin to be coated with water at high speed, and after polymerization, the reactive group-containing resin is obtained from the polymer suspension by cooling. A method of adding and kneading carbon black, reacting the carbon black with a reactive group (grafting the carbon black), cooling and pulverizing;
can be adopted.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins with a benzene ring in their structure have a stronger action as an amphoteric surfactant, so they are difficult to disperse. preferred from the viewpoint of properties and dispersion stability.
Examples of synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin; polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene oxide, Thermoplastic resins such as polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used. The amount of resin coating carbon black is preferably 1 to 30% by mass based on the total amount of carbon black and resin, and coating tends to be sufficient when the amount is equal to or more than the lower limit. On the other hand, by setting it below the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

Carbon black coated with a resin can be used as a light-shielding material for a colored spacer according to a conventional method, and a color filter having this colored spacer as a component can be produced using a conventional method. When such carbon black is used, a colored spacer with a high light shielding rate and a low surface reflectance tends to be achieved at low cost. It is also assumed that coating the carbon black surface with a resin has the effect of sealing Ca and Na into the carbon black.

As the pigment (A) other than carbon black, for example, pigments of various colors used as coloring materials for coloring photosensitive resin compositions can be used.
Examples of such pigments include blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments. These pigments may be organic or inorganic pigments.
The structure of the organic pigment is not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.

Specific examples of the pigment (A) are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 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. Preferably C. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Preferably C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6, 60.

Examples of green pigments include C.I. I.

Pigment Green

1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Preferably C. I. Pigment Green 7, 36, and 58 are mentioned.

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

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

As the purple pigment, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Preferably C. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23 and 29 are mentioned.

As the black pigment, a pigment that exhibits a black color by mixing multiple colored pigments (for example, three colors of red, green, and blue) may be used, or a pigment that exhibits a black color may be used alone. May be used together.

Pigments that can be mixed to prepare black pigments include, for example, Victoria Pure Blue (42595), Auramine O (41000), Cathylone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK70:100 (50240), Erioglaucine X (42080), No. 120/Lionor Yellow (21090), Lionor Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionor Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15:6), Lionor Gen Red GD (Pigment Red 168), Lionor Green 2YS (Pigment Green 36) Can be mentioned.
Note that the numbers in parentheses above mean color index (C.I.).

About other pigments that can be mixed with C. I. Indicated by number, for example, C. I. Yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I.

Orange pigment

36, 43, 51, 55, 59, 61, 64, C.I. I. Red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I.

Violet pigment

19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15:1, 15:4, 22, 60, 64, C.I. I. Green pigment 7, C. I. Brown pigments 23, 25, and 26 are mentioned.

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

As the pigment (A), for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can also be used.

These various pigments can also be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used together, or a blue pigment and a violet pigment can be used together.

(A) The average particle size of the pigment is not particularly limited as long as it can produce the desired color when used as a colored layer of a color filter, and varies depending on the type of pigment used, but is 10 to 100 nm. It is preferably within the range of 10 to 70 nm, and more preferably within the range of 10 to 70 nm. (A) By having the average particle size of the pigment within the above range, the color characteristics of a liquid crystal display device manufactured using a photosensitive resin composition containing the pigment dispersion of the present invention are of high quality. There is a tendency to
The average particle size of carbon black is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more, for example, preferably 20 to 50 nm, more preferably 20 to 60 nm. By setting the average particle size to be less than or equal to the upper limit value, scattering tends to be reduced and deterioration of color properties such as light shielding properties and contrast can be suppressed. Further, by setting the average particle size to the above lower limit or more, the amount of the dispersant (B) does not increase excessively, and the dispersibility tends to be good.

The content ratio of the pigment (A) to the total solid content in the pigment dispersion is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 99% by mass or less, It is more preferably 95% by mass or less, and even more preferably 90% by mass or less. If the content ratio of the pigment (A) is equal to or higher than the lower limit value, the obtained cured product tends to have better light-shielding properties, and if it is lower than the upper limit value, the dispersibility tends to be better.
The above upper and lower limits can be arbitrarily combined. For example, it may be 60-99% by weight, 70-95% by weight, or 80-90% by weight.

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

<(B) Dispersant>
(B) The dispersant finely disperses the pigment (A) and stabilizes the dispersion state.
(B) As the dispersant, a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, for example, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; Polymer dispersants having a class or tertiary amino group; a quaternary ammonium base; and a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred. Particularly preferred are polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine. By using a polymeric dispersant having these basic functional groups, there is a tendency for good dispersibility to be achieved.

Examples of polymeric dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants made of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ether dispersants. Examples include polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Examples of dispersants include, for example, the trade names of EFKA (registered trademark, manufactured by EFKA), DISPERBYK (registered trademark, manufactured by BYK Chemie Co., Ltd.), DISPARBYK (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.). (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.).
One type of polymer dispersant may be used alone, or two or more types may be used in combination.

From the viewpoint of adhesion and linearity, it is preferable that the dispersant contains a urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group. More preferable in terms of gender. Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester and/or polyether bond is preferable.

The weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. By setting it below the above-mentioned upper limit, alkali developability tends to be good even when the pigment concentration is high.
The above upper and lower limits can be arbitrarily combined. For example, it may be between 700 and 100,000, between 700 and 50,000, and between 1,000 and 30,000.

Examples of urethane-based or acrylic-based polymer dispersants include DISPERBYK 160 to 167, 182 series (all urethane-based), DISPERBYK 2000, 2001 (all acrylic-based) (all manufactured by BYK Chemie). DISPERBYK167 and DISPERBYK182 are particularly preferable polymeric dispersants having a basic functional group and a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.

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

Examples of the polyisocyanate compound include aromatic compounds such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolydine diisocyanate. Diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), ω, ω'- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates with aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11- Triisocyanates such as undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanate phenylmethane), tris(isocyanate phenyl) thiophosphate , trimers thereof, water adducts, and polyol adducts thereof. A trimer of organic diisocyanate is preferred, and a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate are more preferred.
One type of polyisocyanate may be used alone, or two or more types may be used in combination.

As a method for producing isocyanate trimers, for example, polyisocyanates are converted into isocyanate groups using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc. After partially trimerizing the polyisocyanate and stopping the trimerization by adding a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate. It will be done.

Examples of compounds with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and compounds in which one terminal hydroxyl group of these compounds has 1 carbon number. Examples include compounds alkoxylated with ~25 alkyl groups.
Compounds having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 may be used alone or in combination of two or more.

Examples of polyether glycol include polyether diol and polyether ester diol.

Examples of polyether diols include compounds obtained by copolymerizing alkylene oxides alone or by copolymerizing them, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol. It will be done.
Polyether ester diols include compounds obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly( oxytetramethylene) adipate.

The polyether glycol is preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.). Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol , 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl Aliphatic glycols such as -2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane , xylylene glycol, aromatic glycols such as bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.), such as polyethylene adipate, polybutylene adipate, polyhexa Methylene adipate, polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol and polymethylvalerolactone. Can be mentioned.
As the polyester glycol, polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator is preferable.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. can be mentioned.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is preferably 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.

In a compound having active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, the hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom, includes, for example, a functional group such as a hydroxyl group, an amino group, or a thiol group. Hydrogen atoms in groups are mentioned, hydrogen atoms in amino groups are preferred, and hydrogen atoms in primary amino groups are more preferred.

The tertiary amino group in a compound having an active hydrogen and a tertiary amino group in the same molecule is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a hetero group such as an imidazole ring or a triazole ring. Examples include ring structures.
Examples of compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, and 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, N,N-dibutyl-1,4-butane Examples include diamines.

When the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzotriazole ring. ring, 5-membered nitrogen-containing hetero rings such as benzoxazole ring, benzothiazole ring, benzothiadiazole ring, 6-membered nitrogen-containing hetero rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. can be mentioned. As the nitrogen-containing heterocycle, an imidazole ring and a triazole ring are preferred.

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

Compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl ) Imidazole and 3-amino-1,2,4-triazole are preferred.
Compounds having active hydrogen and a tertiary amino group in the same molecule may be used singly or in combination of two or more.

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

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

A urethane reaction catalyst may be used in the production of the urethane-based polymer dispersant. Examples of urethanization reaction catalysts include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannath octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, triethylenediamine, etc. Examples include tertiary amines. These may be used alone or in combination of two or more.

It is possible to control the amount of the compound having active hydrogen and a tertiary amino group introduced into the same molecule so that the amine value after the reaction is preferably in the range of 1 to 100 mgKOH/g, more preferably 5 to 95 mgKOH/g. preferable. When the amine value is equal to or higher than the lower limit value, the dispersibility tends to be improved. Furthermore, when the content is below the upper limit, developability tends to be improved.

The amine value is expressed by the amount of base per 1 g of solid content excluding the solvent in the sample and the mass of KOH equivalent to the amount of base, and can be measured by the following method.
Accurately weigh 0.5 to 1.5 g of the sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is subjected to neutralization titration with a 0.1 mol/L HClO ₄ (perchloric acid) acetic acid solution. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.
Amine value [mgKOH/g]=(561×V)/(W×S)
[However, W: weighed amount of dispersant sample [g], V: titration amount at titration end point [mL], S: solid content concentration of dispersant sample [mass %]. ]

When isocyanate groups remain in the polymeric dispersant in the above reaction, it is preferable to consume the isocyanate groups with an alcohol or an amino compound because this will increase the stability of the product over time.

The weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. In particular, it is preferably 30,000 or less. If Mw is equal to or greater than the lower limit, the dispersibility and dispersion stability tend to be good, and if it is equal to or less than the upper limit, the solubility tends to be good.
The above upper and lower limits can be arbitrarily combined. For example, it may be 1000 to 30000, 2000 to 30000, or 3000 to 30000.
In particular, when Mw is 30,000 or less, alkali developability tends to be good even when the pigment concentration is particularly high. Examples of commercially available urethane dispersants include DISPERBYK167 and DISPERBYK182 (manufactured by BYK Chemie).

The content ratio of (A) pigment and (B) dispersant on a mass basis ((A) pigment/(B) dispersant) is preferably 1 or more, more preferably 3 or more, even more preferably 4 or more, and , is preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. If the (A) pigment/(B) dispersant is equal to or higher than the lower limit value, the development solubility tends to be better, and if it is lower than the upper limit value, it is easy to ensure sufficient dispersibility of the (A) pigment. Tend.
The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 50, 3 to 30, or 4 to 15.

The content of the dispersant (B) relative to the total solids in the pigment dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 30% by mass or less. , more preferably 25% by mass or less, and even more preferably 20% by mass or less. (B) If the content ratio of the dispersant is at least the above lower limit, it tends to ensure sufficient dispersibility of the (A) pigment, and if it is below the above upper limit, the proportion of other components can be reduced. There is a tendency that the film formability is better.
The above upper and lower limits can be arbitrarily combined. For example, it may be 5-30% by weight, it may be 10-25% by weight, it may be 15-20% by weight.

<Organic solvent>
As the organic solvent, from the viewpoint of viscosity stability of the pigment dispersion, an organic solvent having a boiling point of 100 to 300°C is preferable, and an organic solvent having a boiling point of 120 to 280°C is more preferable. Here, the boiling point is a value at a pressure of 1013.25 hPa. Hereinafter, all boiling points are the same.

Examples of organic solvents having a boiling point of 100 to 300°C include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
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 Glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

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

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Etherketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

Commercially available organic solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, So Cal 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, diglyme (all product name).
One type of organic solvent may be used alone, or two or more types may be used in combination.

When forming color filter pixels or black matrices by photolithography using a photosensitive resin composition containing a pigment dispersion, an organic solvent with a boiling point of 100 to 250°C is preferable, and an organic solvent with a boiling point of 120 to 230°C is preferable. It is more preferable to use an organic solvent with

As an organic solvent, glycol alkyl ether acetate is recommended because it has a good balance in coating properties, surface tension, etc., has a relatively high solubility of constituent components in the photosensitive resin composition, and has a stable viscosity of the pigment dispersion. Preferably. One type of glycol alkyl ether acetate may be used alone, or two or more types may be used in combination.

Glycol alkyl ether acetates may be used in combination with other organic solvents.
As other organic solvents, glycol monoalkyl ethers are preferred. Propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the constituent components in the photosensitive resin composition.
Since glycol monoalkyl ethers have high polarity, (A) the organic solvent contains glycol monoalkyl ethers from the viewpoint of storage stability related to pigment aggregation and viscosity of the photosensitive resin composition obtained later. In this case, the content of the glycol monoalkyl ethers is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, based on the total mass of the organic solvent.

Glycol alkyl ether acetates and an organic solvent having a boiling point of 200°C or higher (hereinafter sometimes referred to as "high boiling point solvent") may be used in combination. By using a high boiling point solvent in combination, the photosensitive resin composition containing the pigment dispersion becomes difficult to dry, and the uniform dispersion state of the pigment (A) in the composition is prevented from being destroyed by rapid drying. effective. That is, there is an effect of preventing the occurrence of foreign matter defects due to precipitation or solidification of pigments, etc., at the tip of the slit nozzle, for example. The upper limit of the boiling point of the high boiling point solvent is not particularly limited, but is, for example, 300° C. or lower.
In view of the above-mentioned high effects, examples of high boiling point solvents include dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, Examples include 3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate.
One type of high boiling point solvent may be used alone, or two or more types may be used in combination.

The content ratio of the high boiling point solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass, based on the total mass of the organic solvent. If the content ratio of the high boiling point solvent is below the above upper limit, the drying temperature of the composition will be slow, which tends to suppress the occurrence of problems such as poor tact in the vacuum drying process and pin marks in pre-baking in the color filter manufacturing process. There is. If the content of the high boiling point solvent is 0.5% by mass or more, it tends to be possible to suppress the occurrence of foreign matter defects due to precipitation or solidification of pigments, etc., at the tip of the slit nozzle, for example.

In the pigment dispersion of the present invention, the content ratio of the organic solvent can be appropriately selected in consideration of the total solid content and water content in the pigment dispersion.
From the viewpoint of light-shielding properties, the total solid content in the pigment dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total mass of the pigment dispersion. Also, from the viewpoint of viscosity stability and viscosity stability over time, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
The above upper and lower limits can be arbitrarily combined. For example, it may be 10 to 60% by weight, 20 to 50% by weight, or 30 to 40% by weight.

From the viewpoint of viscosity stability and viscosity stability over time, the pigment dispersion of the present invention contains glycol alkyl ether acetates as an organic solvent, and the total solid content in the pigment dispersion is 40% by mass or less. It is more preferable.

When the pigment dispersion of the present invention contains glycol alkyl ether acetates as an organic solvent, the content of glycol alkyl ether acetates in the total organic solvent is preferably 60% by mass or more, and 70% by mass from the viewpoint of viscosity stability. % or more, more preferably 80% by mass or more. Further, from the viewpoint of reducing unevenness during drying of the coating film, the content is preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.
The above upper and lower limits can be arbitrarily combined. For example, it may be 60 to 100% by weight, 70 to 100% by weight, or 80 to 100% by weight.

<(C) Dispersion aid>
The pigment dispersion of the present invention preferably contains (C) a dispersion aid in order to improve the dispersion stability of (A) the pigment.
(C) Examples of the dispersion aid include pigment derivatives. Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolopyrrole. , dioxazine derivatives, and phthalocyanine derivatives and quinophthalone derivatives are preferred.

Examples of substituents on pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups directly on the pigment skeleton, or, for example, alkyl Examples include groups bonded via a group, an aryl group, and a heterocyclic group, and preferably a sulfonic acid group. A plurality of substituents may be substituted on one pigment skeleton.
Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine.
One type of dispersion aid may be used alone, or two or more types may be used in combination.

When the pigment dispersion of the present invention contains (C) a dispersion aid, the content ratio of the (A) pigment and (C) dispersion aid on a mass basis ((A) pigment/(C) dispersion aid) is preferably 10 or more, more preferably 30 or more, even more preferably 50 or more, and is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less. If (A) pigment/(C) dispersion aid is equal to or higher than the above lower limit value, developability tends to be stable and substrate adhesion is more excellent, and if it is equal to or less than the above upper limit value, dispersion stability is better. Tend.
The above upper and lower limits can be arbitrarily combined. For example, it may be 10-200, 30-150, or 50-100.

When the pigment dispersion of the present invention contains the dispersion aid (C), the content of the dispersion aid (C) based on the total solid content of the pigment dispersion is preferably 0.1% by mass or more, and 0.5% by mass. % or more, more preferably 1% by mass or more, further preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less. (C) If the content ratio of the dispersion aid is at least the above lower limit, the dispersion stability tends to be better, and when it is below the above upper limit, the developability is stable and the adhesion to the substrate tends to be better. be.
The above upper and lower limits can be arbitrarily combined. For example, it may be 0.1 to 10% by weight, 0.5 to 5% by weight, or 1 to 3% by weight.

The pigment dispersion of the present invention may further contain components other than (A) pigment, (B) dispersant, (C) dispersion aid, organic solvent, and water, if necessary. Examples of other components include other components in the photosensitive resin composition described below.
The content ratio of other components to the total solid content of the pigment dispersion is preferably 5% by mass or less, more preferably 1% by mass or less, and may be 0% by mass.

The pigment dispersion of the present invention preferably has an absolute value of zeta potential of 50 mV or less, more preferably 48 mV or less, even more preferably 45 mV or less, particularly preferably 40 mV or less. The lower limit is not particularly limited, but is usually 0 mV or more. If the absolute value of the zeta potential is below the upper limit value, the stability of the pigment dispersion is high and there is little pigment aggregation, so the generation of foreign matter is suppressed and the linearity of the pattern tends to improve.
The absolute value of the zeta potential of the pigment dispersion can be measured, for example, with a laser zeta potential meter ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd. using a cell unit for low dielectric constant solvents.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention can be prepared, for example, by mixing optional components such as (A) pigment, (B) dispersant, organic solvent and water, and optionally (C) dispersion aid. Manufactured by a method of dispersion treatment.
The amount of water to be mixed is set so that the final moisture content is within the above range.

Because the pigment (A) is made into fine particles by the dispersion treatment, the coating properties of the pigment dispersion and the photosensitive resin composition containing the same are improved. (A) When the pigment contains a black pigment, the light blocking ability is also improved by the dispersion treatment. In particular, when a polymeric dispersant is used as the dispersant (B), the resulting pigment dispersion and the photosensitive resin composition containing the same are inhibited from increasing in viscosity over time (excellent dispersion stability).

The dispersion treatment can be carried out using a known dispersion treatment device such as a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, or homogenizer. When performing the dispersion treatment with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
Dispersion treatment conditions are not particularly limited, but the temperature is, for example, in the range of 0°C to 100°C, preferably in the range of room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate. A guideline for dispersion is to control the dispersion state of the pigment (A) so that the 20 degree specular gloss (JIS Z8741) of the coating film of the photosensitive resin composition is in the range of 100 to 200. When the gloss of the photosensitive resin composition coating is low, the dispersion treatment is often insufficient and rough pigment particles remain, which may result in insufficient developability, adhesion, resolution, etc. There is sex. Furthermore, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed and a large number of ultrafine particles will be produced, which tends to impair the dispersion stability.
After the dispersion treatment, the obtained dispersion treated product can be filtered using a filter or the like, if necessary, for example, in order to separate the beads used in the dispersion treatment and the pigment dispersion liquid.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains the pigment dispersion of the present invention, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator.

The content ratio of the pigment dispersion liquid of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, in terms of the content ratio of the pigment (A) based on the total solid content of the photosensitive resin composition of the present invention. , more preferably 50% by mass or more, preferably 75% by mass or less, more preferably 70% by mass or less, even more preferably 65% by mass or less. If the content ratio of the pigment (A) is at least the above-mentioned lower limit, the resulting cured product tends to have better light blocking properties, and when it is below the above-mentioned upper limit, the cured product tends to have better formability.
The above upper and lower limits can be arbitrarily combined. For example, it may be 30-75% by weight, it may be 40-70% by weight, it may be 50-65% by weight.

The solid content of the pigment dispersion of the present invention relative to the total solid content of the photosensitive resin composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. If the solid content of the pigment dispersion is equal to or higher than the lower limit, the light-shielding property tends to be better, and if it is lower than the upper limit, the developing solubility tends to be better.
The above upper and lower limits can be arbitrarily combined. For example, it may be 40 to 90% by weight, 50 to 80% by weight, or 60 to 70% by weight.

<(D) Alkali-soluble resin>
(D) The alkali-soluble resin is not particularly limited as long as it exhibits alkali solubility, and includes, for example, resins containing carboxyl groups or hydroxyl groups. More specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, and polyvinylphenol resins. especially,
(D1) Epoxy (meth)acrylate resin (D2) Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making properties.
One type of alkali-soluble resin can be used alone, or two or more types can be used in combination.

<(D1) Epoxy (meth)acrylate resin>
(D1) Epoxy (meth)acrylate resin is a combination of an epoxy compound (epoxy resin) and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. It is a resin obtained by reacting the hydroxyl group generated by the reaction with a compound having two or more substituents capable of reacting with the hydroxyl group, such as a polybasic acid and/or its anhydride.
Before reacting the polybasic acid and/or its anhydride with a hydroxyl group, a compound having two or more substituents that can react with a hydroxyl group is reacted, and then the polybasic acid and/or its anhydride is reacted. The resin obtained by is also included in (D1) epoxy (meth)acrylate resin.
A resin obtained by reacting a compound having a functional group that can further react with the carboxy group of the resin obtained by the above reaction is also included in the epoxy (meth)acrylate resin (D1).
Epoxy (meth)acrylate resin has a chemical structure that substantially does not have an epoxy group, and is not limited to "(meth)acrylate," but it uses an epoxy compound (epoxy resin) as a raw material, and , "(meth)acrylate" is a typical example, so it is named this way according to common usage.

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

<Epoxy (meth)acrylate resin (D1-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid and/or its anhydride. Alkali soluble resin.
<Epoxy (meth)acrylate resin (D1-2)>
Adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with polyhydric alcohol, polybasic acid and/or its anhydride Alkali-soluble resin obtained by.

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Examples of the types of epoxy resins used as raw materials include cresol novolak epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, trisphenolmethane epoxy resin, biphenyl novolak epoxy resin, and naphthalene. Novolak-type epoxy resins, epoxy resins that are reaction products of polyaddition products of dicyclopentadiene and phenol or cresol, and epihalohydrin, adamantyl group-containing epoxy resins, and fluorene-type epoxy resins can be suitably used. Those having an aromatic ring can be more preferably used.

Examples of epoxy resins include bisphenol A type epoxy resins (for example, "jER (registered trademark, the same applies hereinafter) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), bisphenol A type epoxy resins, etc. Epoxy resins obtained by the reaction of alcoholic hydroxyl groups of epoxy resins with epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point 76°C)), bisphenol F type resins (for example, manufactured by Mitsubishi Chemical Co., Ltd.) "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Nippon Chemical Co., Ltd.), epoxy resins obtained by the reaction of the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, Nippon Chemical Co., Ltd.) "NER-7406" manufactured by Yakusha (epoxy equivalent: 350, softening point 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (For example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Company, "DEN-438" manufactured by Dow Chemical Company), (o, m, p -) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same applies)-501", "EPPN-502", manufactured by Nippon Kayaku Co., Ltd.), EPPN-503''), alicyclic epoxy resin (Daicel's ``Celoxide (registered trademark, hereinafter the same applies) 2021P'', ``Celoxide EHPE''), epoxy made by glycidylating phenolic resin by reaction of dicyclopentadiene and phenol. Resins (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4) can be suitably used. can. Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as an epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as an epoxy resin represented by the following general formula (B2). "NC-3000" by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B4), and manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4) An example of this is the "ESF-300" manufactured by Manufacturer.

In formula (B1), a is an average value and represents a number from 0 to 10, and R ¹¹¹ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. group, phenyl group, naphthyl group, or biphenyl group. Note that the plurality of R ^111s present in one molecule may be the same or different.

In formula (B2), b1 and b2 are each independently an average value and represent a number from 0 to 10, and R ¹²¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. ~10 cycloalkyl, phenyl, naphthyl, or biphenyl groups. Note that the plurality of R ^121s present in one molecule may be the same or different.

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

In formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group that may have a substituent, a hydrogen atom, or an adamantyl group that has a substituent. represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or a phenyl group optionally having a substituent, and * represents a bond.

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

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

Examples of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 -(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2 -(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropylmaleic acid, 2- (meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipate, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-( meth) Acryloyloxybutyl maleic acid (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to acrylic acid; or hydroxy A monomer in which an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), or maleic acid (anhydride) is added to alkyl (meth)acrylate, pentaerythritol tri(meth)acrylate; (meth)acrylic Examples include acid dimer.
Among these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, it is possible to react an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150°C in the presence of an esterification catalyst. can. As the esterification catalyst used here, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used. can.

Each component of the epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be selected one by one and used. , two or more types may be used in combination.
The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents per equivalent of epoxy group in the epoxy resin, and Preferably it is 0.7 to 1.1 equivalent. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit value or more, it is possible to suppress the shortage of the amount of unsaturated groups introduced, and the subsequent The reaction with basic acids and/or their anhydrides also tends to be sufficient. By setting it below the above upper limit, it is possible to suppress the residual of unreacted substances of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group, and it is easy to obtain good curing characteristics. A trend is observed.

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

The addition reaction of a polybasic acid and/or its anhydride can be carried out using a known method. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of carboxylic acid esters. The amount of polybasic acid and/or its anhydride component added so that the acid value of the produced carboxyl group-containing epoxy (meth)acrylate resin is preferably 10 to 150 mgKOH/g, more preferably 20 to 140 mgKOH/g. It is preferable to control. When the amount is equal to or more than the lower limit, the alkali developability tends to be improved. There is a tendency for curing performance to be improved by setting the amount to be less than or equal to the upper limit value.

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

By using a polyhydric alcohol, it is possible to increase the molecular weight of the epoxy (meth)acrylate resin (D1) and introduce branches into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.

Examples of the carboxyl group-containing epoxy (meth)acrylate resin include, in addition to those mentioned above, the resin described in Korean Patent Publication No. 10-2013-0022955.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, It is even more preferably 3,000 or more, particularly preferably 4,000 or more, particularly preferably 5,000 or more. Further, it is preferably 30,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less. By setting the amount to be at least the lower limit, it tends to be possible to prevent the solubility in the developer from becoming too high. By setting it below the above-mentioned upper limit, there is a tendency that the solubility in the developer tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 1000 to 30000, 1500 to 20000, 1500 to 15000, or 2000 to 15000.

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

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

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

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

<(d1-I) Epoxy (meth)acrylate resin>

( ^R12 )
In formula (d1-I), R ¹² represents a divalent hydrocarbon group which may have a substituent.
Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.

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

Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
The divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 12, it may be from 1 to 10, it may be from 2 to 10.
Examples of the divalent cyclic aliphatic group include rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, dicyclopentadiene, and dicyclopentane ring. An example is a group obtained by removing two hydrogen atoms from . From the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring is preferable.

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

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be between 4 and 20, between 5 and 15, and between 6 and 10.

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

Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, non-substitution is preferred.

The group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 10, it may be from 1 to 5, it may be from 1 to 3, it may be from 2 to 3.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 10 or less, more preferably 5 or less, and even more preferably 3 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 10, it may be from 1 to 5, it may be from 1 to 3, it may be from 2 to 3.

Examples of groups connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the following formulas (d1-I-A) to (d1-IF). Examples include groups such as From the viewpoint of rigidity of the skeleton and hydrophobicization of the membrane, a group represented by the following formula (d1-IA) is preferable.

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

The benzene ring in formula (d1-I) may be further substituted with any substituent.
Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of patterning properties, it is preferable that no substitution be made.

The partial structure represented by formula (d1-I) is preferably a partial structure represented by the following general formula (d1-I-1) from the viewpoint of ease of synthesis.

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

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

The benzene ring in formula (d1-I-1) may be further substituted with any substituent. As the substituent, the groups listed for the benzene ring in formula (d1-I) can be preferably employed.

(d1-I) The partial structure represented by formula (d1-I-1) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, when ^R A partial structure of atoms and a partial structure in which R ^X is a polybasic acid residue may coexist.

(d1-I) The number of partial structures represented by formula (d1-I) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable, and 15 or less is more preferable. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 20, 1 to 15, or 3 to 15.

(d1-I) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, most preferably 5,000 or more, preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. When the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive coloring composition tends to be good. When the content is below the upper limit, the solubility in the developer tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1000-30000, 1500-2000, 1500-15000, or 2000-1500.

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

Specific examples of the (d1-I) epoxy (meth)acrylate resin are listed below. Note that * in the examples indicates a bond.

<(d1-II) Epoxy (meth)acrylate resin>

( ^R14 )
In formula (d1-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. When the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 10, it may be from 1 to 5, it may be from 1 to 3, it may be from 2 to 3.
The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. When the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be between 4 and 40, between 4 and 30, between 6 and 20, and between 8 and 15.
Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of the residual film rate and resolution of the photosensitive coloring composition, an adamantane ring is preferred.

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

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.

Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. A linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be between 1 and 25, between 3 and 20, and between 6 and 15.

Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. , an isobutyl group, a sec-butyl group, and a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. When the content is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate. In addition, by setting the amount to be below the upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 10, it may be from 1 to 5, it may be from 1 to 3, it may be from 2 to 3.
Examples of divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. can be mentioned. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be between 4 and 30, between 5 and 20, and between 6 and 15.

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

Examples of groups linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the above-mentioned formulas (d1-I-A) to (d1-IF). The following groups are mentioned. From the viewpoint of skeleton rigidity and membrane hydrophobization, a group represented by formula (d1-IC) is preferred.

The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, if one hydrogen atom of an aliphatic group or an aromatic ring group is Examples include an embodiment in which the aliphatic group is substituted with a hydrocarbon group, and an embodiment in which a cyclic hydrocarbon group that is a side chain includes one of the carbon atoms of the aliphatic group.

(R ¹⁵ , R ¹⁶ )
In formula (d1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. A linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be between 1 and 20, between 3 and 15, and between 6 and 10.

Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
The divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve.
The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 12, or from 2 to 10.
Examples of the divalent cyclic aliphatic group include two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and dicyclopentadiene ring. Examples include groups that have been removed. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.

(m, n)
In formula (d1-II), m and n each independently represent an integer of 0 to 2. When the amount is at least the lower limit, patterning becomes more appropriate and surface roughness that occurs during development tends to be less likely to occur, and when the amount is at most the upper limit, the developability tends to be good. From the viewpoint of developability, m and n are preferably 0. From the viewpoint of appropriate patterning and suppressing surface roughness that occurs during development, m and n are preferably 1 or more.

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

In formula (d1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in formula (d1-II), and R ^α is a monovalent group that may have a substituent. It represents a cyclic hydrocarbon group, p represents an integer of 1 or more, and * represents a bond. The benzene ring in formula (d1-II-1) may be further substituted with any substituent.

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

The number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Further, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 6, it may be from 1 to 4, it may be from 1 to 3, it may be from 2 to 3.
The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be between 4 and 40, between 4 and 30, between 6 and 20, and between 8 and 15.
Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.

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

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.

p represents an integer of 1 or more, preferably 2 or more. Moreover, 3 or less is preferable. For example, 1 to 3 are preferable, and 2 to 3 are more preferable. When the amount is equal to or more than the lower limit, the degree of film curing and the remaining film rate tend to be good. When the amount is below the upper limit, developability tends to be improved.

From the viewpoint of strong film hardening, R ^α is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.

The benzene ring in formula (d1-II-1) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more.
From the viewpoint of patterning properties, it is preferable that no substitution be made.

Specific examples of the partial structure represented by formula (d1-II-1) are listed below.

The partial structure represented by the formula (d1-II) is preferably a partial structure represented by the following general formula (d1-II-2) from the viewpoint of skeleton rigidity and membrane hydrophobization.

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

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

The number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Moreover, 10 or less is preferable, and 5 or less is more preferable. When the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 10, or from 2 to 5.
The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. By setting it above the lower limit value, there is a tendency to suppress roughness of the film surface during development. By setting it below the above-mentioned upper limit, deterioration of sensitivity and film thinning during development can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be 4-40, 6-35, or 8-30.
Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of film loss during development and resolution, an adamantane ring is preferred.

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

From the viewpoints of suppressing film thinning and resolution, R ^β is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group. On the other hand, from the viewpoint of patterning properties, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

The benzene ring in formula (d1-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more.
Further, the two benzene rings in formula (d1-II-2) are connected via R ^β , and may be further connected via a substituent to form a tricyclic structure. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH ₂ -. For example, to form a tricyclic structure by connecting via -O- means that the carbon atoms at the ortho position of the carbon atom bonded to R ^β on each benzene ring are connected via -O-, It means forming a xanthene skeleton.
From the viewpoint of patterning properties, it is preferable that no substitution be made. Furthermore, from the viewpoint of making film thinning less likely to occur, methyl group substitution is preferable.

Specific examples of the partial structure represented by formula (d1-II-2) are listed below. Note that * in the examples indicates a bond.

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

In formula (d1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in formula (d1-II), and R ^Z represents a hydrogen atom or a polybasic acid residue. represent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid. Note that one more OH group may be removed and shared with R ^Z in another molecule represented by formula (d1-II-3). That is, a plurality of formulas (d1-II-3) may be connected via R ^Z.
Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid is more preferable. They are phthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

(d1-II) The partial structure represented by formula (d1-II-3) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types. For example, when R ^Z is hydrogen There may be a mixture of atoms and those in which R ^Z is a polybasic acid residue.

(d1-II) The number of partial structures represented by formula (d1-II) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit value, deterioration of sensitivity and film thinning can be easily suppressed, and resolution tends to improve. The above upper and lower limits can be arbitrarily combined. For example, it may be from 1 to 20, it may be from 1 to 15, it may be from 3 to 10.

(d1-II) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, particularly preferably 5000 or more. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. When the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive coloring composition tends to be good. When the content is below the upper limit, the solubility in the developer tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1000-10000, 1500-10000, 1500-8000, 2000-8000, 2000-7000.

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

The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more.
Further, a part of the above-mentioned carboxyl group-containing epoxy (meth)acrylate resin may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth)acrylate resin and another binder resin may be used in combination. In this case, the proportion of the carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferable to set it as 80 mass % or more, and it is especially preferable to set it as 100 mass % or less.

<(D2) Acrylic copolymer resin>
(D) As the alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use (D2) acrylic copolymer resin, and the resin described in Japanese Patent Application Publication No. 2014-137466 is preferably used. be able to.

(D2) As the acrylic copolymer resin, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (d2-1)") and other copolymers Examples include copolymers with possible ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomers (d2-2)").

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

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

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

Examples of the copolymer of unsaturated monomer (d2-1) and unsaturated monomer (d2-2) include Japanese Patent Application Publication No. 7-140654, Japanese Patent Application Publication No. 8-259876, Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Unexamined Japanese Patent Application No. 11-174224, Unexamined Japanese Patent Application No. 11-258415, Unexamined Japanese Patent Application No. 2000-56118, Copolymers disclosed in Japanese Patent Application Publication No. 2004-101728 can be mentioned.
The copolymer of the unsaturated monomer (d2-1) and the unsaturated monomer (d2-2) can be produced by a known method, for example, Japanese Patent Application Publication No. 2003-222717, The structure, Mw, and Mw/Mn (Mn is the number average molecular weight) can also be controlled by the methods disclosed in Japanese Patent Application Publication No. 2006-259680 and International Publication No. 2007/029871. .

The resins described in International Publication No. 2016/194619 and International Publication No. 2017/154439 may be used.

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

(E) As the photopolymerizable compound, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenically monomer is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, particularly preferably 6 or more, and preferably 10. The number is more preferably 8 or less. When the amount is equal to or more than the lower limit, the photosensitive resin composition tends to have high sensitivity, and when it is equal to or less than the upper limit, curing shrinkage during polymerization tends to be reduced.
The above upper and lower limits can be arbitrarily combined. For example, the number may be 2 to 10, 3 to 10, 4 to 10, 5 to 8, or 6 to 8.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a polyhydroxy compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylic acid obtained by replacing the acrylate of these exemplary compounds with methacrylate. Mention may also be made of esters, such as itaconic esters in place of itaconate, crotonic esters in place of cronate or maleic esters in place of maleate.

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

Other examples of polyfunctional ethylenic monomers used in the present invention include, for example, reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic ester. urethane (meth)acrylates such as those obtained by oxidation; epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; phthal Allyl esters such as acid diallyl; vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used alone or in combination of two or more.

(E) The content ratio of the photopolymerizable compound is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, and 50% by mass or less based on the total solid content of the photosensitive resin composition. It is more preferably 30% by mass or less, even more preferably 20% by mass or less, most preferably 10% by mass or less, further preferably 1% by mass or more, and more preferably 5% by mass or more. (E) When the content of the photopolymerizable compound is at most the above-mentioned upper limit, the permeability of the developer into the exposed area becomes appropriate, and a good image tends to be obtained. By being at least the above lower limit, photocuring by ultraviolet irradiation tends to be improved and alkali developability also tends to be good.
The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 90% by weight, 1 to 70% by weight, 1 to 50% by weight, 5 to 30% by weight, 5 to 20% by weight. It may well be between 5 and 10% by weight.

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

(F) Photopolymerization initiators include, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open No. 59-152396 and Japanese Patent Application Publication No. 61-151197; Hexaarylbiimidazole derivatives described in Japanese Patent Publication No. 56118; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No. 10-39503; radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in Japanese Patent Publication No.

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

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

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

Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.

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

(F) As the photopolymerization initiator, oxime derivatives (oxime ester compounds and ketooxime ester compounds) are preferable from the viewpoint of sensitivity. Among the oxime derivatives, oxime ester compounds are preferred from the viewpoint of adhesion to the substrate. When using an alkali-soluble resin containing a phenolic hydroxyl group, there may be a disadvantage in terms of sensitivity.
The oxime ester compound photopolymerization initiator has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so it is highly sensitive even in small amounts, and is highly sensitive to thermal reactions. It is stable against light, and it is possible to design a highly sensitive photosensitive resin composition in a small amount. In particular, in the case of an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, This structural characteristic is well expressed and is more preferable. Currently, the market demands a thin black matrix with a high degree of light shielding, and the pigment concentration is also increasing. This is particularly effective in such situations.

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

In formula (22), R ²² is an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or an alkanoyl group having 3 to 25 carbon atoms, each of which may be substituted. -8 cycloalkanoyl group, C3-20 alkoxycarbonylalkanoyl group, C8-20 phenoxycarbonylalkanoyl group, C3-20 heteroaryloxycarbonylalkanoyl group, C2-10 amino It represents an alkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

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

Note that R ^21a may form a ring with R ^21b , and the linking group thereof is an alkylene group having 1 to 10 carbon atoms which may have a substituent, a polyethylene group (-(CH=CH) _r -), a polyethynylene group (-(C≡C) _r -), or a combination thereof (r is an integer from 0 to 3).
R ^22a represents the same group as R ²² in formula (22).
R ²² in formula (22) and R ^22a in formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a cycloalkanoyl group having 3 to 8 carbon atoms. can be mentioned.

R ^21a in formula (23) is preferably an unsubstituted linear alkyl group such as a methyl group, ethyl group, or propyl group or a cycloalkylalkyl group, or propyl substituted with an N-acetyl-N-acetoxyamino group. Examples include groups.
Preferably, R ^21b in formula (23) includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenyl sulfide group.

As a photopolymerization initiator for an oxime ester compound, a compound in which R ^21b in formula (23) is an optionally substituted carbazolyl group is more preferable for the reasons described above. Furthermore, an optionally substituted aryl group having 6 to 25 carbon atoms, an optionally substituted arylcarbonyl group having 7 to 25 carbon atoms, an optionally substituted heteroaryl group having 5 to 25 carbon atoms, a substituted A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms, which may optionally be a nitro group, is preferred. Particularly preferred is a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group. Further, these groups are desirably bonded to the 3-position of the carbazolyl group.

Commercially available photopolymerization initiators of oxime ester compounds include, for example, OXE-02 manufactured by BASF, and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Powerful Electronics.

Examples of photopolymerization initiators for oxime ester compounds include the following.

Examples of ketooxime ester compounds include compounds containing a structural moiety represented by the following general formula (24), preferably ketoxime ester compounds represented by the following general formula (25).

In formula (24), R ²⁴ has the same meaning as R ²² in formula (22).

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

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^23a may form a ring together with R ^23b , and the linking group thereof is an alkylene group having 1 to 10 carbon atoms, each of which may have a substituent, or a polyethylene group (-(CH=CH) _r -) , a polyethynylene group (-(C≡C) _r -), or a group formed by combining these (r is an integer from 0 to 3).

R ^24a is an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, each of which may be substituted; Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group.
R ²⁴ in formula (24) and R ^24a in formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a cycloalkanoyl group having 3 to 8 carbon atoms. , an aryloyl group having 7 to 20 carbon atoms.

Preferably, R ^23a in formula (25) includes an unsubstituted ethyl group, propyl group, butyl group, and an ethyl group or propyl group substituted with a methoxycarbonyl group.
R ^23b in formula (25) preferably includes an optionally substituted carbazoyl group and an optionally substituted phenyl sulfide group.
Examples of ketooxime ester compounds include the following.

Commercially available photopolymerization initiators for ketoxime ester compounds include, for example, OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Powerful Electronics Co., Ltd.

The oxime ester compound and the ketooxime ester compound are compounds known per se, and are, for example, compounds described in Japanese Patent Application Publication No. 2000-80068 and Japanese Patent Application Publication No. 2006-36750.
One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, Anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1 -Hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone, etc. acetophenone derivatives; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; p- Benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine such as 9,10-dimethylbenzphenazine Derivatives: Anthrone derivatives such as benzanthrone are included.
As the photopolymerization initiator, oxime ester derivatives are particularly preferred for the reasons mentioned above.

(F) The content ratio of the photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more based on the total solid content of the photosensitive resin composition. It is preferably 4% by mass or more, particularly preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less. . (F) If the content ratio of the photopolymerization initiator is equal to or higher than the lower limit value, the sensitivity tends to improve, and if the content ratio is lower than the upper limit value, the solubility of the unexposed area in the developer tends to improve. .
The above upper and lower limits can be arbitrarily combined. For example, it may be 1-30% by weight, it may be 1-20% by weight, it may be 2-15% by weight, it may be 3-10% by weight, it may be 4-8% by weight. good.

<Sensitizing dye>
(F) A sensitizing dye corresponding to the wavelength of the image exposure light source can be used in combination with the photopolymerization initiator (F), if necessary, for the purpose of increasing the sensitivity. Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335. Coumarin dyes having a heterocycle as described in Japanese Patent Publication No. 3-239703, 3-ketocoumarin compounds described in Japanese Patent Application Publication No. 5-289335, as described in Japanese Patent Application Publication No. 6-19240 Pyrromethene dyes, and others, Japanese Patent Publication No. 47-2528, Japanese Patent Application Publication No. 54-155292, Japanese Patent Application Publication No. 45-37377, Japanese Patent Application Publication No. 1984-84183, Japan Japanese Patent Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, Japanese Patent Application Publication No. 59-56403, Japanese Patent Application Publication No. 2-69 dialkylaminobenzene skeletons described in Japanese Patent Application Laid-open No. 57-168088, Japanese Patent Application Publication No. 5-107761, Japanese Patent Application Publication No. 5-210240, and Japanese Patent Application Publication No. 4-288818. Examples include dyes having the following.

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 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 More preferred are p-dialkylaminophenyl group-containing compounds such as 4,4'-dialkylaminobenzophenone.
One type of sensitizing dye may be used alone, or two or more types may be used in combination.

The content ratio of the sensitizing dye is not particularly limited, but is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 10% by mass, based on the total solid content of the photosensitive resin composition. preferable.

<Organic solvent>
The photosensitive resin composition of the present invention may contain an organic solvent not derived from the pigment dispersion of the present invention in order to adjust the solid content and coatability. Examples of the organic solvent not derived from the pigment dispersion of the present invention include the same organic solvents as those in the pigment dispersion.
In the photosensitive resin composition of the present invention, the content rate of the other organic solvent can be appropriately selected in consideration of the content rate of the total solid content in the photosensitive resin composition.

The total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and 10% by mass with respect to the total mass of the photosensitive resin composition from the viewpoint of light shielding properties. The above is more preferable, and from the viewpoint of development solubility and patterning properties, it is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.
The above upper and lower limits can be arbitrarily combined. For example, it may be 5 to 40% by weight, 8 to 30% by weight, or 10 to 25% by weight.

<Other ingredients in the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition of the present invention includes (A) coloring materials other than pigments, thiols, adhesion improvers, coating properties improvers, development improvers, ultraviolet absorbers, and antioxidants. Agents, etc. can be blended as appropriate.

(Other color materials)
(A) Examples of coloring materials other than pigments include dyes.
Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

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

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. An example is Disperse Blue 60.
Examples of phthalocyanine dyes include C.I. I. Pad Blue 5 is an example. Examples of quinoneimine dyes include C.I. I. Basic Blue 3, C. I. Basic Blue 9 is an example. Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 is mentioned. Examples of nitro dyes include C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. An example is Disperse Yellow 42.

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

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

When the photosensitive resin composition of the present invention contains thiols, the content of thiols is preferably 0.1% by mass or more, and 0.3% by mass based on the total solid content of the photosensitive resin composition. The content is more preferably 0.5% by mass or more, further preferably 10% by mass or less, and more preferably 5% by mass or less. If the content ratio of thiols is at least the above lower limit value, there is a tendency to suppress a decrease in sensitivity, and if it is below the above upper limit value, there is a tendency that storage stability tends to be good.
The above upper and lower limits can be arbitrarily combined. For example, it may be 0.1 to 10% by weight, 0.3 to 10% by weight, or 0.5 to 5% by weight.

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

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

In formulas (g1), (g2), and (g3), R ⁵¹ each independently represents a hydrogen atom or a methyl group, l and l' each independently represent an integer of 1 to 10, and m each independently represents 1 or 2. Or 3.
Other adhesion improvers include, for example, TEGO*Add Bond LTH (manufactured by Evonik).
One type of adhesion improver may be used alone, or two or more types may be used in combination.

When the photosensitive resin composition of the present invention contains an adhesion improver, the content ratio of the adhesion improver in the photosensitive resin composition is not particularly limited, but is 0.5% relative to the total solid content of the photosensitive resin composition. 01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. It is preferably 1.5% by mass or less, particularly preferably 1.5% by mass or less. If the content of the adhesion improver is at least the lower limit, the adhesion will tend to improve, and if the content is at most the upper limit, the developability will tend to improve.
The above upper and lower limits can be arbitrarily combined. For example, it may be 0.01 to 5% by weight, it may be 0.01 to 3% by weight, it may be 0.1 to 2% by weight, and it may be 0.5 to 1.5% by weight. good.

(Applicability improver)
The photosensitive resin composition of the present invention may contain a coating properties improver to improve coating properties.
Examples of the coating property improver include surfactants. As the surfactant, for example, anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferred since they are less likely to adversely affect various properties, and fluorine surfactants and silicone surfactants are more preferred from the viewpoint of coatability.

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

When the photosensitive resin composition of the present invention contains a coating property improver, the content ratio of the coating property improving agent in the photosensitive resin composition is not particularly limited, but is based on the total solid content of the photosensitive resin composition. It is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and preferably at most 1.0% by mass, more preferably at most 0.7% by mass, and even more preferably at most 0.5% by mass. Particularly preferred is 0.3% by mass or less. If the content ratio of the coating property improver is equal to or greater than the lower limit value, coating uniformity tends to improve, and if the content ratio is equal to or less than the upper limit value, resist sensitivity tends not to decrease.
The above upper and lower limits can be arbitrarily combined. For example, it may be 0.01-1.0% by weight, it may be 0.01-0.7% by weight, it may be 0.05-0.5% by weight, it may be 0.05-0. It may be 3% by mass.

<Physical properties of photosensitive resin composition>
The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from this point of view, it is preferable that the photosensitive resin composition exhibits a black color. Further, the optical density (OD) per 1 μm of film thickness of the coating film is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 2.5 or more, even more preferably 3.0 or more, and 4 A value of .0 or more is particularly preferred, and a value of 4.5 or more is most preferred. If the OD is greater than or equal to the lower limit, sufficient light-shielding properties tend to be ensured. The upper limit of OD is not particularly limited, but is, for example, 6.0. The OD may be, for example, 1.0 to 6.0, 2.0 to 6.0, 2.5 to 6.0, 3.0 to 6.0. It may be between 4.0 and 6.0, and between 4.5 and 6.0.

<Method for manufacturing photosensitive resin composition>
The photosensitive resin composition of the present invention includes, for example, the pigment dispersion of the present invention, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator, an organic solvent as necessary, and others. It can be manufactured by mixing the following ingredients.
The temperature during mixing is, for example, 20 to 30°C.
After mixing, the resulting photosensitive resin composition may be filtered using a filter or the like, if necessary.

The photosensitive resin composition of the present invention can be used as a resist for members constituting color filters, such as pixels and black matrices. When the photosensitive resin composition of the present invention is used for a black matrix, it contains a black coloring material such as a black pigment.
The photosensitive resin composition of the present invention can also be used as a resist for colored spacers.
The photosensitive resin composition of the present invention can also be used to form partition walls, particularly partition walls for partitioning organic layers of an organic electroluminescent device. Examples of the organic layer of the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on the hole injection layer, as described in Japanese Patent Application Publication No. 2016-165396. An example is an organic layer.

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

[Black Matrix]
The black matrix made of the cured product of the present invention will be explained according to its manufacturing method.
The black matrix made of the cured product of the present invention can be obtained by, for example, applying the photosensitive resin composition of the present invention on a support on which the black matrix is to be provided, drying it, and applying a photomask on the dried coating film. It can be formed by a method of placing the film, exposing it to light through a photomask (image exposure), developing it, and carrying out a curing treatment if necessary.

(1) Support The material of the support for forming the black matrix is not particularly limited as long as it has appropriate strength, and transparent substrates are mainly used. Examples of the material for the transparent substrate include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, Examples include thermosetting resin sheets such as poly(meth)acrylic resins and various types of glasses. Among these, glass and heat-resistant resin are preferred from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO may be formed on the surface of the transparent substrate. It is also possible to form on a support other than a transparent substrate, for example, a TFT array.
To improve surface properties such as adhesion, the support may be treated with corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, or thin film formation treatment of various resins such as urethane resins, as necessary. You may go.
The thickness of the transparent substrate is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm. Further, when performing a thin film formation treatment of various resins, the film thickness is preferably in the range of 0.01 to 10 μm, more preferably 0.05 to 5 μm.

(2) Formation of black matrix (2-1) Application of photosensitive resin composition The application of the photosensitive resin composition for the black matrix onto the support can be performed, for example, by spinner method, wire bar method, flow coating method, etc. This can be carried out by a die coating method, a roll coating method, or a spray coating method. According to the die coating method, the amount of coating liquid used is significantly reduced, there is no influence of mist etc. that adheres when using the spin coating method, and the generation of foreign matter is suppressed, which is preferable from a comprehensive viewpoint. .

The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. By setting it below the above-mentioned upper limit, pattern development tends to be facilitated, and gap adjustment in the liquid crystal cell formation process also tends to be facilitated. When the amount is equal to or more than the lower limit value, it tends to be easier to express a desired color.

(2-2) Drying of coating film The coating film after coating the photosensitive resin composition on the support is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected depending on the type of liquid medium (organic solvent, water) contained in the photosensitive resin composition, the performance of the dryer used, etc. For example, the time is selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200°C, preferably in the range of 30 seconds to 3 minutes at a temperature of 50 to 130°C.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate; however, if the drying temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and causing poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed within a reduced pressure chamber without increasing the temperature.

(2-3) Exposure Image exposure is performed by overlaying a photomask on the coating film of the photosensitive resin composition and irradiating light with a wavelength ranging from the ultraviolet region to the visible region through this photomask. A negative mask pattern is typically used as a photomask. At this time, if necessary, in order to prevent a decrease in sensitivity of the coating film due to oxygen, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the coating film. The light source used for image exposure is not particularly limited. Examples of the light source include lamp light sources such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and a carbon arc. When using irradiation with light of a specific wavelength, an optical filter can also be used.

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

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus. Inorganic alkaline compounds such as acid potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds.
The alkaline compounds may be used alone or in a mixture of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

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

There are no particular restrictions on the conditions for development processing. The developing temperature is preferably 10 to 50°C, more preferably 15 to 45°C, even more preferably 20 to 40°C. The developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, an ultrasonic developing method, or the like.

(2-5) Curing Treatment Examples of the curing treatment include thermosetting treatment and photocuring treatment, with thermosetting treatment being preferred.
As for the heat curing treatment conditions, the temperature is selected in the range of 100 to 280°C, preferably in the range of 150 to 250°C, and the time is selected in the range of 5 to 60 minutes.

The height of the black matrix formed as described above is preferably 0.5 to 5 μm, more preferably 0.8 to 4 μm. Furthermore, the optical density (OD) per 1 μm of thickness is preferably 2.0 or more, more preferably 2.5 or more, even more preferably 3.0 or more, and particularly preferably 3.2 or more.

[Color filter]
Containing a color material of one color among red (R), green (G), and blue (B) on a transparent substrate provided with a black matrix using the same process as in (2-1) to (2-5) above. After applying the photosensitive resin composition and drying, a photomask is placed on the coating film, and a pixel image is formed by image exposure and development through this photomask, and if necessary, thermal curing or photocuring, Create a colored layer. By performing this operation for each of the three color photosensitive resin compositions of R, G, and B, a color filter can be formed. These orders are not limited to the above order.

(2-6) Formation of transparent electrodes The color filter can be used as a part of components of color displays, liquid crystal display devices, etc. by forming transparent electrodes such as ITO on the image as it is.
In order to improve surface smoothness and durability, a top coat layer of polyamide, polyimide, etc. can be provided on the image, if necessary. In some applications, for example, in applications using a planar alignment drive system (IPS mode), a transparent electrode may not be formed.

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

[Bulkhead]
The partition wall made of the cured product of the present invention will be explained according to its manufacturing method.
The partition wall made of the cured product of the present invention can be obtained, for example, by applying the photosensitive resin composition of the present invention onto a support on which the partition wall is to be provided, drying it, and placing a photomask on the dried coating film. It can be formed by exposing through a photomask (image exposure), developing, and, if necessary, curing.

(3-1) Support As the support for forming the partition walls, the same support as the above-mentioned support for forming the black matrix can be used.

(3-2) Formation of partition walls In the method of forming partition walls, the specific methods of coating the photosensitive resin composition on the support, drying method, exposure method, development method, and curing treatment are as follows: Formation of the black matrix described above A similar method can be adopted.

The size, shape, etc. of the partition walls are appropriately adjusted depending on the specifications of the organic electroluminescent device to which they are applied, but the height of the partition walls formed from the photosensitive resin composition is preferably about 0.5 to 10 μm.

[Organic electroluminescent device]
Various organic electroluminescent devices are manufactured using a support provided with partition walls manufactured by the method described above.
For example, the method for forming an organic electroluminescent device is not particularly limited, but preferably, the organic electroluminescent device is manufactured by forming partition walls on a support by the method described above, and then forming an organic layer such as a pixel. be done.
Methods for forming the organic layer include vapor deposition, in which a functional material is sublimated in a vacuum, and deposited within an area surrounded by partition walls on a substrate, and wet methods, such as casting, spin coating, and inkjet printing. One example is the process.

Types of organic electroluminescent devices include bottom emission type and top emission type.
In the bottom emission type, for example, partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition walls. Ru. On the other hand, in the top emission type, for example, partition walls are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the partition walls. Created by
Examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

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

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

When using an organic electroluminescent device as a pixel in an image display device, it is necessary to prevent light from the light-emitting layer of one pixel from leaking to other pixels, and to prevent the reflection of external light if the electrodes are made of metal. In order to prevent the image quality from deteriorating due to this, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent device.
In an organic electroluminescent device, since electrodes are provided on the upper and lower surfaces of the partition walls, from the viewpoint of insulation, the partition walls preferably have high resistance and low dielectric constant. Therefore, when using a coloring agent to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment that has high resistance and low dielectric constant.

[Image display device]
The image display device of the present invention includes the cured product of the present invention.
Examples of the image display device of the present invention include the image display device provided with the above-mentioned black matrix or partition wall.
The image display device is not particularly limited as long as it is a device that displays images or videos, and includes liquid crystal display devices and organic EL displays, which will be described later.

[Liquid crystal display device]
The liquid crystal display device according to the present invention can be manufactured using, for example, the color filter having the black matrix described above. Note that there are no particular restrictions on the formation order or formation position of color pixels and black matrices.

Generally, a liquid crystal display device forms an alignment film on a color filter, scatters spacers on this alignment film, and then attaches it to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell. Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. Gravure printing and/or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After the alignment film is hardened by thermal baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface condition that allows adjustment of the tilt of the liquid crystal.

The spacer used has a size that corresponds to the gap with the opposing substrate, and is preferably 2 to 8 μm. It is also possible to form a photospacer (PS) of a transparent resin film on the color filter substrate by photolithography and use this instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The bonding gap with the counter substrate varies depending on the use of the liquid crystal display device, but is preferably in the range of 2 to 8 μm. After bonding to the counter substrate, parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the inside of the chamber. . The degree of reduced pressure within the liquid crystal cell is preferably 1×10 ⁻⁷ to 1×10 ⁻² Pa, more preferably 1×10 ⁻⁶ to 1×10 ⁻³ Pa. Further, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. It is preferable to keep the temperature under reduced pressure for 10 to 60 minutes. It is then immersed in liquid crystal. A liquid crystal display device (panel) is completed by curing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected and sealing it with a UV curing resin.

The type of liquid crystal is not particularly limited, and it may be any conventionally known liquid crystal such as aromatic, aliphatic, polycyclic compounds, etc., such as lyotropic liquid crystal, thermotropic liquid crystal, etc. Nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, etc. are known as thermotropic liquid crystals, but any of them may be used.

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

When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. A color filter is prepared in which a black matrix (not shown) is provided between pixels 20, and an organic light emitter 500 is formed on the color filter via an organic protective layer 30 and an inorganic oxide film 40. By stacking, the organic EL element 100 can be manufactured. Note that at least one of the pixels 20 and the black matrix was produced using the photosensitive resin composition of the present invention. The organic light emitter 500 can be laminated by sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the top surface of the color filter. , a method of bonding the organic light emitter 500 formed on a separate substrate onto the inorganic oxide film 40, and the like. Using the organic EL element 100 produced in this way, for example, the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, written by Shizushi Tokito, Chinaya Adachi, and Hideyuki Murata), etc. An organic EL display can be manufactured using this method.

Note that the color filter in the present invention is applicable to both passive drive type organic EL displays and active drive type organic EL displays.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
The components of the pigment dispersion liquid and photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

<Pigment-1>
"RAVEN1060" (carbon black) manufactured by BIRLA CARBON.
<Dispersant-1>
"DISPERBYK-167" (urethane polymer dispersant) manufactured by BYK Chemie.
<Dispersion aid-1>
"S12000-S" (copper phthalocyanine sulfonate derivative) manufactured by Lubrizol.
<Organic solvent>
Propylene glycol monomethyl ether acetate (PGMEA).

<Alkali-soluble resin-1>
A resin obtained in a synthesis example described later was used.
<Photopolymerizable compound-1>
"KAYARAD DPHA" (multifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
<Photopolymerization initiator-1>
"TR-PBG-304" manufactured by Changzhou Strong Electronics New Materials Co., Ltd. (oxime ester compound having a carbazole skeleton).
<Surfactant-1>
"Megafac F554" (fluorine surfactant) manufactured by DIC.
<Additive-1>
"X-12-1048" (polyfunctional acrylic silane) manufactured by Shin-Etsu Chemical Co., Ltd.

240 parts by mass of the epoxy compound having 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 paramethoxyphenol. The mixture was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the mixture was reacted at 90° C. with stirring for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 51.6 parts of tetrahydrophthalic anhydride (THPA) were added to the reaction solution obtained by the above reaction. The mass part was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105°C while stirring to react. An alkali-soluble resin having a Mw) of 2500 was obtained.

<Preparation of pigment dispersion>
Pigment-1, dispersant-1, dispersion aid-1, PGMEA, and water listed in Table 1 were mixed to have the mass ratio and water content listed in Table 1 to obtain a mixed solution. Note that the blending ratio of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the solvent derived from the dispersion aid.
Beads were added to this mixed solution and dispersed in a paint shaker at a temperature of 25 to 45° C. for 6 hours. Zirconia beads with a diameter of 0.5 mm were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to obtain dispersion liquids 1 to 8.

<Evaluation of pigment dispersion>
The following evaluations were performed on the obtained dispersions 1 to 8.

[viscosity]
The viscosity of each of Dispersions 1 to 8 at 23°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80L). The results are shown in Table 1.

[Filterability]
5 mL of each of dispersions 1 to 8 was filtered using a Teflon tube equipped with a filter (Millipore 1.2 μm, manufactured by Merck & Co., Ltd.) at room temperature by applying a pressure of 0.004 MPa to 0.006 MPa, and from the start of filtration. The time (seconds) until completion was measured. The value was defined as filterability. The results are shown in Table 1.
Dispersion 7 had a high viscosity and the filterability could not be measured, so further evaluation was not performed.

[Viscosity stability]
After storing the obtained dispersions 1 to 8 at 35° C. for 30 days, the viscosity of each dispersion at 23° C. was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80L). The results are shown in Table 1.

[Zeta potential measurement]
Using a laser zeta electrometer ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd., Dispersion 1 was diluted 1,500 times with PGMEA and then injected into a cell for a low dielectric constant solvent, and the zeta potential was measured at an applied voltage of 300V.

The absolute value of the zeta potential of Dispersion 1 was 37 mV.

<Preparation of photosensitive resin composition>
Each component shown in Table 2 was added to the dispersions 1 to 6 and 8 prepared above so that the solid content ratio of each component in the total solid content of the photosensitive resin composition was as shown in Table 2, and propylene Glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate (MBA) and diethylene glycol monoethyl ether acetate (EDGAC) were added to the photosensitive resin composition so that the total solid content was 14% by mass, and furthermore, in the solvent. PGMEA/MBA/EDGAC was added so that the mass ratio was 68/30/2, and the mixture was stirred and dissolved to obtain photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 2.

<Evaluation of photosensitive resin composition>
The following evaluations were performed for each of the obtained photosensitive resin compositions.

[Peeling test]
At an ambient temperature of 23°C and a humidity of 50%, 20 mm of the vertical tip of a glass test piece measuring 100 mm in length x 5 mm in width x 0.7 mm in thickness was immersed in the photosensitive resin composition at a speed of 12.5 mm/sec. After that, the glass test piece was held in that position for 4 seconds, taken out from the photosensitive resin composition at a speed of 12.5 mm/s, and held vertically with the tip of the glass test piece facing down, at an ambient temperature of 23°C and humidity. The drying process was repeated 250 times under conditions of 55% and wind speed of 0.5±0.2 seconds.
Thereafter, the tip of the glass test piece (the part immersed in the photosensitive resin composition) was observed at four locations in total, including both widthwise ends (ridgeline areas) on the front and back sides, and no deposits were observed. The following criteria were used to evaluate the number of ridgeline areas. The results are shown in Table 2.
A: No deposits are observed on the ridge line.
B: Deposits are observed at one ridgeline site.
C: Deposits are observed on two or more ridgeline areas.
Moreover, the ridgeline portion of the glass test piece of each example is shown in FIG. In FIG. 2, optical microscope images of two ridgeline sites are shown side by side for each of Examples 1 to 5 and Comparative Examples 1 to 2. A line extending vertically near the center of each of the two side-by-side optical microscope images is a ridgeline portion, and the area inside each ridgeline portion (center side in the figure) is the tip of the glass test piece.

[Dissolution time]
A photosensitive resin composition was applied onto a glass substrate using a spin coater so that the film thickness after heat curing was 1.2 μm, and after drying under reduced pressure at 100 Pa for 60 seconds, it was dried on a hot plate at 100° C. for 120 seconds. Dry. The obtained coating film was exposed to ultraviolet light having an intensity of 60 mW/cm ² at a wavelength of 365 nm using a photomask having openings with a line width of 1 μm to 30 μm in 1 μm increments. Exposure treatment was performed so that the amount of light was 40 mJ/cm ² .
Subsequently, shower development was performed at 23° C. and a water pressure of 0.05 MPa using a developer consisting of a 0.04% by mass KOH (potassium hydroxide) aqueous solution, and then the development was stopped with pure water and washed with a washing spray. I washed it. The time when patterning was visible during shower development was measured as the dissolution time. The results are shown in Table 2.

[Minimum contact]
In evaluating the dissolution time, the glass substrate after shower development is observed with an optical microscope, and among the patterns (line patterns) remaining on the glass substrate with no chipping and good linearity, a photo corresponding to the one with the smallest width is taken. The value of the line width (μm) of the mask opening was defined as the minimum adhesion. It can be said that the smaller this value is, the better the substrate adhesion is. The results are shown in Table 2.

[Line width]
The glass substrate after shower development for evaluation of dissolution time was observed with an optical microscope, and the width of the pattern corresponding to the opening of the photomask with a line width of 30 μm was measured. The results are shown in Table 2.

From the results in Table 1, it was shown that when the water content of the pigment dispersion was less than 1.2% by mass, the viscosity and filterability immediately after the pigment dispersion was prepared were good. On the other hand, when the water content was 1.2% by mass or more, rapid thickening was observed and viscosity stability was shown to deteriorate. The reasons for this are that oil-liquid separation from the organic solvent occurred due to the increased moisture content, and that the solubility of the dispersant in the organic solvent decreased, making it impossible to uniformly adsorb it onto the pigment. is possible.
It was also shown that when the water content of the pigment dispersion was less than 0.95% by mass, the viscosity stability after 30 days of storage was also good. The reasons for this are that oil-liquid separation from organic solvents gradually progressed during the storage period as the water content increased, and that the solubility of the dispersant in organic solvents decreased, resulting in uniform dispersion of pigments. It is possible that adsorption is no longer possible.
From the results in Table 2, it was shown that when the water content of the pigment dispersion liquid was 0.14% by mass or less, the peel test results deteriorated. Furthermore, it was found that when the moisture content exceeds 0.14% by mass, the peel test results were good and there was no influence on solubility, minimum adhesion, and line width. The reason for this is that if the moisture content is optimal, the dispersion stability of the pigment over time is good and no aggregates are formed, and in addition, moisture suppresses rapid drying of the photosensitive resin composition. This is thought to be due to the fact that pigment aggregation was suppressed.

10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims

A pigment dispersion containing (A) a pigment, (B) a dispersant, an organic solvent, and water,
The pigment (A) contains carbon black,
A pigment dispersion liquid having a moisture content of 0.15% by mass or more and 0.9% by mass or less.
The pigment dispersion according to claim 1, having a moisture content of 0.2% by mass or more and 0.7% by mass or less.
The pigment dispersion according to claim 1, wherein the content ratio of the pigment (A) to the total solid content of the pigment dispersion is 60% by mass or more.
The pigment dispersion according to claim 1, wherein the content ratio ((A) pigment/(B) dispersant) of the (A) pigment and the (B) dispersant on a mass basis is 4 or more.
The pigment dispersion according to claim 1, further comprising (C) a dispersion aid.
The pigment dispersion according to claim 5, wherein the content ratio ((A) pigment/(C) dispersion aid) of the (A) pigment and the (C) dispersion aid on a mass basis is 10 or more.
A photosensitive resin composition containing the pigment dispersion according to any one of claims 1 to 6, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator.
The photosensitive resin composition according to claim 7, wherein the content ratio of the pigment (A) to the total solid content of the photosensitive resin composition is 30% by mass or more.
A cured product obtained by curing the photosensitive resin composition according to claim 7.
A black matrix consisting of the cured product according to claim 9.
An image display device comprising the cured product according to claim 9.