Photosensitive resin composition, cured product, partition, organic electroluminescent element, color filter, and image display device

Abstract

Provided is a photosensitive resin composition which can form a partition wall having a small taper angle and an excellent residual film rate after a firing process, while having a small amount of smoke during the firing process. This photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated compound, wherein the (C) ethylenically unsaturated compound has a structure represented by formula (2).

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, cured products, spacers, organic electroluminescent elements, color filters, and image display devices.

[0002] This application claims priority based on Japanese Patent Application No. 2023-42534, filed in Japan on March 17, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] Liquid crystal displays (LCDs) utilize the property of switching the alignment of liquid crystal molecules by turning on / off voltage. Furthermore, most of the components constituting an LCD cell are formed using methods employing photosensitive compositions, such as photolithography.

[0004] This photosensitive composition is easy to form fine structures and easy to process substrates for large screens, for which its application range has been further expanded.

[0005] Image display devices that include organic electroluminescent elements (also known as organic EL) have excellent visibility and responsiveness, such as contrast and viewing angle. They can achieve low power consumption, thinness and light weight, and flexibility of the display body, and are therefore attracting attention as the next generation of flat panel displays (FPDs).

[0006] An organic electroluminescent element has a structure in which an organic layer comprising a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which is transparent. An image display device is a means of displaying images by driving a panel in which organic electroluminescent elements are configured for each pixel.

[0007] Previously, such organic electroluminescent devices were manufactured by forming spacers (banks) on a substrate and then stacking light-emitting layers or various functional layers in the area surrounded by the spacers.

[0008] In order to form a film such as a light-emitting layer in an area surrounded by spacers, the main application is the vapor deposition method, which involves sublimating the material in a vacuum and attaching it to the substrate to form a film.

[0009] In recent years, film formation methods using wet processes such as casting, spin coating, and inkjet printing have attracted attention. In particular, inkjet printing can reduce film thickness unevenness in the case of large-area fabrication and can achieve high precision in displays, reduce material usage, and increase yield by separating the coating during the coating process. Therefore, it is suitable as a film formation method for organic layers in large panels.

[0010] As a method for easily forming spacers, a photolithography method using a photosensitive composition is known. Furthermore, as a method for imparting light-blocking properties to the spacers and suppressing light leakage between pixels, a method of containing a colorant in the photosensitive composition is known.

[0011] Patent Document 1 describes a photosensitive coloring resin composition that has high opacity and low dielectric constant by using a specific organic black pigment and dispersant.

[0012] Furthermore, Patent Document 2 discloses a photosensitive coloring resin composition that effectively suppresses degassing by using a specific organic black pigment and an alkali-soluble resin, and is used in the spacer wall application of organic electroluminescent elements.

[0013] Existing technical documents

[0014] Patent documents

[0015] Patent Document 1: International Publication No. 2015 / 46178

[0016] Patent Document 2: International Publication No. 2018 / 101314 Summary of the Invention

[0017] The problem that the invention aims to solve

[0018] The process involves placing the substrate in a high-temperature chamber during the formation of spacers using photolithography. In recent years, the gas generated during this firing process, known as fumes, has been found to adhere to the anode, potentially causing an increase in the driving voltage of the organic light-emitting element and unevenness in the emitting surface, resulting in poor display quality.

[0019] Furthermore, in organic electroluminescent elements, when the cathode, which serves as a common electrode, is set by vapor deposition, the smaller the cone angle of the spacer wall (the angle between the support and the solidified material in the cross section of the solidified material), the less likely it is to cause wire breakage, and the better the productivity of the organic electroluminescent element. However, sometimes it is not possible to obtain a good cone angle when manufacturing the spacer wall.

[0020] Furthermore, if the residual film rate of the spacer wall obtained after firing is low, the obtained spacer wall may also be easily affected by changes in the developing process and firing process, resulting in unstable quality.

[0021] The inventors conducted research and found that the photosensitive coloring resin composition described in Patent Document 1 produces a large amount of smoke during firing, which poses a problem in practical use.

[0022] Furthermore, it was found that when the photosensitive resin composition with improved photocurability was designed to reduce the amount of smoke, a good cone angle could not be obtained.

[0023] Furthermore, it was found that when a thermosetting material was added to the photosensitive resin composition to reduce the amount of smoke, the photosensitivity decreased, thereby reducing the residual film rate of the spacer wall after firing.

[0024] The present invention was made in view of the above circumstances, and its object is to provide a photosensitive resin composition that produces less smoke during firing and can form spacers with small cone angles and excellent residual film yield after firing. Furthermore, the present invention aims to provide an organic electroluminescent element and an image display device having such spacers.

[0025] Solution for solving the problem

[0026] The inventors conducted in-depth research and discovered that the above-mentioned technical problems could be solved by using specific olefinic unsaturated compounds in the photosensitive resin composition, thus completing the present invention.

[0027] That is, the main idea of ​​this invention is as follows.

[0028] [1] A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an olefinic unsaturated compound.

[0029] The (C) olefinic unsaturated compound has a structure represented by the following general formula (2).

[0030] [Chemical Formula 1]

[0031]

[0032] (In equation (2), R) 4 ~R 6 Each independently represents an alkylene group, which is optionally truncated midway by an ether-like oxygen atom. R 7 ~R 9 Each can independently represent a hydrogen atom or a methyl group.

[0033] [2] According to the photosensitive resin composition of [1], wherein the molecular weight of the (C) olefinic unsaturated compound is 500 to 1000.

[0034] [3] The photosensitive resin composition according to [1] or [2], wherein the photosensitive resin composition further comprises (D) a colorant and (E) a dispersant.

[0035] [4] The photosensitive resin composition according to [3], wherein the (D) colorant contains an organic black pigment (D-1).

[0036] [5] The photosensitive resin composition according to [4], wherein the organic black pigment (D-1) contains a benzodifuranone-based organic black pigment.

[0037] [6] According to the photosensitive resin composition of [5], wherein the benzodifuranone-based organic black pigment contains an organic black pigment as a compound represented by the following general formula (D-1-1), its geometric isomer, its salt, or a salt of its geometric isomer.

[0038] [Chemical Formula 2]

[0039]

[0040] (In formula (D-1-1), R) 611 and R 616 Each can independently represent a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R 612 R 613 R 614 R 615 R 617 R 618 R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, and R. 621 COOH, COOR 621 COO - CONH2, CONHR 611 CONR 621 R 622 CN, OH, OR 621 COCR 621 、OOCNH2、OOCNHR 621 OOCNR 621 R 622 NO2, NH2, NHR 621 NR 621 R 622 , NHCOR 622 NR 621 COR 622 N=CH2, N=CHR 621 N = CR 621 R 622 SH, SR 621 SOR 621 SO2R 621 SO3R 621 SO3H, SO3 - SO2NH2, SO2NHR 621 or SO2NR 621 R 622 Choose freely R612 and R 613 R 613 and R 614 R 614 and R 615 R 617 and R 618 R 618 and R 619 and R 619 and R 620 At least one combination of the groups is optionally directly bonded to each other or optionally bonded through an oxygen atom, a sulfur atom, NH or NR atom. 621 Bridges are bonded together; R 621 and R 622 Each of the following can be independently represented as an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, a cycloalkenyl group with 3 to 12 carbon atoms, or an alkynyl group with 2 to 12 carbon atoms.

[0041] [7] A photosensitive resin composition according to any one of [3] to [6], wherein the content of the (D) colorant is 5% by mass or more relative to the total solids content of the photosensitive resin composition.

[0042] [8] A photosensitive resin composition according to any one of [1] to [7], wherein the content of the (C) olefin unsaturated compound relative to the total amount of the (C) olefin unsaturated compound and the (C2) unsaturated compound other than the (C) olefin unsaturated compound is 4% by mass or more and 90% by mass or less.

[0043] [9] A photosensitive resin composition according to any one of [1] to [8], wherein the proportion of the (A) alkali-soluble resin is 100 parts by mass or more relative to the total amount of the (C) olefinic unsaturated compound and (C2) unsaturated compounds other than (C) olefinic unsaturated compound.

[0044]

[10] A photosensitive resin composition according to any one of [1] to [9], wherein the photosensitive resin composition is used to form a spacer wall.

[0045]

[11] A cured product, which is a cured product obtained by curing a photosensitive resin composition according to any one of [1] to

[10] .

[0046]

[12] A spacer wall formed from a solidified material according to

[11] .

[0047]

[13] An organic electroluminescent element having a spacer wall according to

[12] .

[0048]

[14] A color filter having spacers according to

[12] and comprising luminescent nanocrystals.

[0049]

[15] An image display device having a spacer according to

[12] .

[0050] Invention Effects

[0051] According to the present invention, a photosensitive resin composition can be provided that produces less smoke during firing and can form spacers with small cone angles and excellent residual film yield after firing. Furthermore, organic electroluminescent elements, color filters, and image display devices incorporating such spacers can be provided. Attached Figure Description

[0052] Figure 1 This is a schematic cross-sectional view of an example of a color filter having the spacer wall of the present invention. Detailed Implementation

[0053] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented by various modifications within the scope of its spirit.

[0054] In this invention, "(meth)acrylic acid" refers to "acrylic acid and / or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

[0055] In this invention, "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid or a (co)polymer containing (meth)acrylate having a carboxyl group.

[0056] In this invention, "total solids content" refers to all components other than solvents contained in the photosensitive resin composition or colorant dispersion. Even if the components other than solvents are liquids at room temperature, they are not contained in the solvent but are contained in the total solids content.

[0057] "(Co)polymer" refers to both homopolymer and copolymer, while "acid (anhydride)" and "...acid (anhydride)" refer to both acid and its anhydride.

[0058] In this invention, "monomer" is a term relative to so-called high molecular weight substances (polymers), and includes not only monomers in the narrow sense, but also dimers, trimers, and oligomers.

[0059] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0060] In this invention, unless otherwise specified, "amine value" refers to the amine value converted from the effective solid content, which is expressed as the mass of KOH equivalent to the amount of alkali per 1g of dispersant solid content.

[0061] It should be noted that the determination method will be described later. Unless otherwise specified, "acid value" refers to the acid value converted from the effective solid content, calculated by neutralization titration.

[0062] Regarding pigments, "CI" refers to the Color Index.

[0063] In this specification, the percentages and parts expressed as “mass” have the same meaning as the percentages and parts expressed as “weight”.

[0064] [Photosensitive Resin Composition]

[0065] The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an olefinic unsaturated compound.

[0066] <(A) Alkali-soluble resin>

[0067] The alkali-soluble resin (A) in this invention is not particularly limited to any resin exhibiting alkali solubility. Examples include resins containing carboxyl or hydroxyl groups. More specifically, examples include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, phenolic varnish resins, polyvinylphenol resins, and resins containing an isocyanuric acid backbone. In particular, from the viewpoint of excellent plate-making performance, (A1) epoxy (meth)acrylate resins, (A2) resins containing an isocyanuric acid backbone, and (A3) acrylic copolymer resins are preferred. They can be used individually or in combination of two or more.

[0068] <(A1) Epoxy (meth)acrylate resins>

[0069] The (A1) epoxy (meth)acrylate resin in this invention is an (A) alkali-soluble resin, which is obtained by further reacting the hydroxyl groups generated by the reaction of an epoxy compound (epoxy resin) with α,β-unsaturated monocarboxylic acid and / or α,β-unsaturated monocarboxylic acid esters having carboxyl groups in the ester moiety with compounds having two or more substituents that can react with hydroxyl groups, such as polybasic acids and / or their anhydrides.

[0070] Before reacting the above-mentioned polybasic acid and / or its anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with a hydroxyl group is reacted, and then the polybasic acid and / or its anhydride is reacted, and the resulting resin is also included in (A1) epoxy (meth) acrylate resins.

[0071] The resin obtained by further reacting the carboxyl group of the resin obtained through the above reaction with a compound having a reactive functional group is also included in (A1) epoxy (meth) acrylate resins.

[0072] Epoxy (meth)acrylate resins do not substantially possess epoxy groups in their chemical structure and are not limited to "(meth)acrylates," but since epoxy compounds (epoxy resins) are raw materials and "(meth)acrylates" are representative examples, they are named in this way according to convention.

[0073] As the (A1) epoxy (meth) acrylate resin used in this invention, from the viewpoint of developability and reliability, the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2) (hereinafter sometimes referred to as "carboxyl-containing epoxy (meth) acrylate resin") are preferred.

[0074] From the viewpoint of residual film yield, epoxy (meth)acrylate resins having aromatic rings in the main chain are more preferable as (A1) epoxy (meth)acrylate resins. The presence of aromatic rings in the main chain increases developer resistance and heat resistance, thus tending to result in a higher residual film yield for the spacer walls after firing.

[0075] <Epoxy (meth)acrylate resin (A1-1)>

[0076] A base-soluble resin is obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to an epoxy resin, and then reacting it with a polybasic acid and / or its anhydride.

[0077] <Epoxy (meth)acrylate resin (A1-2)>

[0078] A base-soluble resin is obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to an epoxy resin, and then reacting it with polyols and polyacids and / or their anhydrides.

[0079] Here, epoxy resin refers to the raw material compound that is formed before the resin is cured by heat. As this epoxy resin, it can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epoxy halide. As the phenolic compound, a compound having divalent or more phenolic hydroxyl groups is preferred; it can be a monomer or a polymer.

[0080] The types of epoxy resins used as raw materials may preferably include: cresol varnish-type epoxy resin, phenol varnish-type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, biphenol varnish-type epoxy resin, naphthol varnish-type epoxy resin, epoxy resins that are the reaction products of the addition polymerization reaction of dicyclopentadiene with phenol or cresol and epoxy halopropane, adamantyl-containing epoxy resins, and fluorene type epoxy resins. Epoxy resins with aromatic rings in the main chain may be more preferred.

[0081] As epoxy resins, the following are preferably used: bisphenol A type epoxy resins (e.g., "jER828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resins obtained by reacting the alcohol hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resins obtained by reacting the alcohol hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resins, and biphenyl glycidyl ether (e.g., ... Examples include: Mitsubishi Chemical's "YX-4000"; phenolic varnish epoxy resins (e.g., Nippon Kayaku Co.'s "EPPN-201", Mitsubishi Chemical's "EP-152", "EP-154", Dow Chemical's "DEN-438"); (ortho, meta, para)cresol varnish epoxy resins (e.g., Nippon Kayaku Co.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"); triphenol methane epoxy resins (e.g., Nippon Kayaku Co.'s "EPPN-501", "EPPN-502", "EPPN-503"); alicyclic epoxy resins (e.g., Daicel's "CELLOXIDE 2021P"). EHPE), epoxy resins obtained by glycidylating phenolic resins obtained from the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (A1α) to (A1δ). Specifically, examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is represented by the following general formula (A1α); "NA2000" and "NA2500" manufactured by Nippon Kayaku Co., Ltd., which are represented by the following general formula (A1β); "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd., which is represented by the following general formula (A1γ); and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., which is represented by the following general formula (A1δ).

[0082] [Chemical Formula 3]

[0083]

[0084] In formula (A1α), a is the average value, representing a number from 0 to 10, and R... 111 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. It should be noted that multiple R groups present in a molecule... 111 They can be the same or different.

[0085] [Chemical Formula 4]

[0086]

[0087] In equation (A1β), b1 and b2 are average values, each independently representing a number from 0 to 10, and R... 121 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. It should be noted that multiple R groups present in a molecule... 121 They can be the same or different.

[0088] [Chemical Formula 5]

[0089]

[0090] In formula (A1γ), X represents a linking group represented by the following general formula (A1γ-1) or (A1γ-2). The molecular structure contains more than one adamantane structure. c represents 2 or 3.

[0091] [Chemical Formula 6]

[0092]

[0093] In equations (A1γ-1) and (A1γ-2), R 131 ~R 134 and R 135 ~R 137 Each of the following independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group optionally having a substituent having 1 to 12 carbon atoms, or a phenyl group optionally having a substituent; * indicates a bond.

[0094] [Chemical Formula 7]

[0095]

[0096] In equation (A1δ), p and q each independently represent integers from 0 to 4, and R 141 and R 142 Each independently represents an alkyl or halogen atom having 1 to 4 carbon atoms, R 143 and R 144Each of the two groups independently represents an alkylene group with 1 to 4 carbon atoms, and x and y independently represent integers greater than 0.

[0097] As the epoxy resin, it is preferred to use an epoxy resin represented by any one of the formulas (A1α) to (A1δ).

[0098] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with a carboxyl group include: (meth)acrylic acid, crotonic acid, ortho, meta, or p-vinylbenzoic acid, α-haloalkyl, alkoxy, halogen, nitro, and cyano-substituted monocarboxylic acids; 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl succinate, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, and phthalic acid... Monomers of 2-(meth)acryloyloxypropyl formate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrogenated phthalate, 2-(meth)acryloyloxybutyl phthalate, and 2-(meth)acryloyloxybutyl maleate; monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid; or monomers obtained by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl methacrylate or pentaerythritol tri(meth)acrylate; and (meth)acrylic acid dimers. From the perspective of photosensitivity, (meth)acrylic acid is preferred.

[0099] As a method for adding α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups to epoxy resin, known methods can be used. For example, α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups can be reacted with epoxy resin in the presence of an esterification catalyst at a temperature of 50–150°C. Examples of esterification catalysts used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, as well as quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0100] Regarding the components of epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups, and esterification catalyst, one of each component may be selected for use, or two or more components may be used together.

[0101] The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group used is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, relative to the epoxy group content of the epoxy resin. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group to the lower limit or above, insufficient introduction of unsaturated groups can be suppressed, and the subsequent reaction with polybasic acids and / or their anhydrides tends to become sufficient. By setting it to the upper limit or below, the residue of unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group can be suppressed, and a tendency to easily improve curing properties can be confirmed.

[0102] Examples of polybasic acids and / or their anhydrides include, for example: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and their anhydrides.

[0103] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyl tetracarboxylic acid, and their anhydrides. Tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and their anhydrides are particularly preferred.

[0104] The addition reaction of polybasic acids and / or their anhydrides can be carried out using known methods. The reaction can continue under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to epoxy resins to obtain the target product. The amount of addition of the polybasic acid and / or its anhydride is preferably such that the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is 10–150 mg KOH / g, more preferably 20–140 mg KOH / g. Setting the value above the lower limit tends to improve alkali developability. Setting the value below the upper limit tends to improve curing performance.

[0105] In addition reactions of polybasic acids and / or their anhydrides, polyfunctional alcohols (polyols) such as trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol can be added to introduce multi-branched structures. In this case, the mixing order of the polybasic acid and / or its anhydride with the polyfunctional alcohol is not particularly restricted. By heating, the polybasic acid and / or its anhydride undergo an addition reaction relative to any hydroxyl group present in the mixture of the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester with a carboxyl group and the polyfunctional alcohol.

[0106] By using polyols, there is a tendency to increase the molecular weight of (Al) epoxy (meth)acrylate resins, introduce branches into the molecule, and achieve a balance between molecular weight and viscosity. Furthermore, there is a tendency to increase the introduction rate of acid groups into the molecule, making it easier to achieve a balance between sensitivity, adhesion, etc.

[0107] In addition to the resins mentioned above, other examples of carboxyl-containing epoxy (meth)acrylate resins include those described in Korean Patent Publication No. 10-2013-0022955.

[0108] The weight-average molecular weight (Mw) of the carboxyl-containing epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC) and converted to polystyrene, is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Furthermore, it is preferably 30000 or less, more preferably 20000 or less, and even more preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and even more preferably 2000 to 15000. By setting it to the lower limit or above, there is a tendency to suppress excessive solubility in the developer. By setting it to the upper limit or below, there is a tendency to easily achieve good solubility in the developer.

[0109] The acid value of the carboxyl-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, further preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20–200 mg KOH / g, more preferably 60–150 mg KOH / g, further preferably 80–130 mg KOH / g, and even more preferably 100–130 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting it to the upper limit or below, there is a tendency for better residual film yield.

[0110] (A1) The chemical structure of the epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of developability and reliability, it is preferred to contain an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (A1-I) (hereinafter, sometimes abbreviated as "(A1-I) epoxy (meth)acrylate resin") and / or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (A1-II) (hereinafter, sometimes abbreviated as "(A1-II) epoxy (meth)acrylate resin").

[0111] [Chemical Formula 8]

[0112]

[0113] In formula (A1-I), R 11 R represents a hydrogen atom or a methyl group. 12 This indicates a divalent hydrocarbon group that may optionally have substituents, k indicates 1 or 2, and * indicates a bonded bond.

[0114] The benzene ring in formula (A1-I) can be further substituted with any substituents.

[0115] [Chemical Formula 9]

[0116]

[0117] In formula (A1-II), R 13 Each can independently represent a hydrogen atom or a methyl group, R 14 R represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following groups independently represents a divalent aliphatic group that may optionally have substituents; m and n each independently represent integers from 0 to 2; and * represents a bond.

[0118] <(A1-I) Epoxy (Meth)acrylate Resins>

[0119] [Chemical Formula 10]

[0120]

[0121] In formula (A1-I), R 11 R represents a hydrogen atom or a methyl group. 12 This indicates a divalent hydrocarbon group that may optionally have substituents, k indicates 1 or 2, and * indicates a bonded bond.

[0122] The benzene ring in formula (A1-I) can be further substituted with any substituents.

[0123] (R 12 )

[0124] In the above formula (A1-I), R 12 This indicates a divalent hydrocarbon group that may optionally have substituents.

[0125] As divalent hydrocarbon groups, examples include divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0126] Divalent aliphatic groups can be categorized as linear, branched, or cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Furthermore, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 1 to 10. By setting the value above the lower limit, there is a tendency to obtain a strong film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, to achieve a high residual film rate after development, and to improve resolution.

[0127] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeletal rigidity, methylene is preferred.

[0128] Examples of divalent branched aliphatic groups include those with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains.

[0129] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 12 or less, more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred. By setting it to the lower limit or above, there is a tendency to form a robust film and improve substrate adhesion. By setting it to the upper limit or below, there is a tendency to suppress sensitivity degradation, achieve high residual film rate after development, and improve resolution.

[0130] Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from rings such as cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, dicyclopentadiene, and dicyclopentane. From the viewpoint of skeletal rigidity, groups obtained by removing two hydrogen atoms from dicyclopentadiene, dicyclopentane, or adamantane are preferred.

[0131] Substituents that can be optionally present as divalent aliphatic groups include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0132] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Furthermore, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 20 is preferred, more preferably 5 to 15, and even more preferably 6 to 10. By setting the value above the lower limit, there is a tendency to obtain a robust film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0133] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon ring group can be a monocyclic or fused ring. Examples of divalent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, which have two free valences. Chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring.

[0134] Aromatic heterocycles, as divalent aromatic heterocyclic groups, can be monocyclic or fused rings. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazolium rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazolium rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolinium rings, quinoxaline rings, phenanthridine rings, naphthalene-intercalated diazabenzene rings, quinazoline rings, quinazolineone rings, and azurite rings.

[0135] From the viewpoint of patterning properties, benzene rings or naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0136] Substituents optionally present in the divalent aromatic cyclic group include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of developing solubility, unsubstituted groups are preferred.

[0137] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0138] The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to obtain a strong film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, to achieve a high residual film rate after development, and to improve resolution.

[0139] The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to obtain a robust film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0140] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups, examples include groups represented by the following formulas (A1-IA) to (A1-IF). In the following formulas (A1-IA) to (A1-IF), * indicates a bond. From the viewpoint of rigidity of the framework and hydrophobicity of the membrane, groups represented by the following formula (A1-IA) are preferred.

[0141] [Chemical Formula 11]

[0142]

[0143] In formula (A1-I), k represents 1 or 2. From the viewpoint of adhesion and printing quality, k is preferably 1. From the viewpoint of sensitivity, k is preferably 2. Furthermore, (A1-I) epoxy (meth)acrylate may contain both a partial structure with k = 1 and a partial structure with k = 2.

[0144] The benzene ring in formula (A1-I) can be further substituted with any substituents.

[0145] Examples of substituents include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more.

[0146] From a design perspective, the preferred option is the unsubstituted one.

[0147] From the viewpoint of ease of synthesis, the partial structure represented by formula (A1-I) is preferably the partial structure represented by the following general formula (A1-I-1).

[0148] [Chemical Formula 12]

[0149]

[0150] In formula (A1-I-1), R 11 R 12 And k has the same meaning as equation (A1-I), R X * indicates a hydrogen atom or a polybasic acid residue, and * indicates a bond.

[0151] The benzene ring in formula (A1-I-1) can be further substituted with any substituents.

[0152] A polybasic acid residue refers to a monovalent or divalent group obtained by removing one or two OH groups 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, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

[0153] From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyl tetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyl tetracarboxylic acid are more preferred.

[0154] The benzene ring in formula (A1-I-1) can be further substituted with any substituents. As substituents, the substituents listed in relation to the benzene ring in formula (A1-I) are preferred.

[0155] (A1-I) An epoxy (meth)acrylate resin molecule may contain one or more structural components represented by formula (A1-I-1), for example, R X Partial structure of hydrogen atom and R X The partial structures of polyacid residues can coexist.

[0156] The number of partial structures represented by formula (A1-I) contained in one molecule of an epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Furthermore, it is preferably 20 or less, and even more preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. Preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15. By setting the value above the lower limit, there is a tendency to easily obtain a strong film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0157] The weight-average molecular weight (Mw) of the (A1-I) epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC) and converted to polystyrene, is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and preferably 30000 or less, more preferably 20000 or less, and even more preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and even more preferably 2000 to 15000. By setting it to the lower limit or above, there is a tendency for the residual film rate to become better. By setting it to the upper limit or below, there is a tendency for the solubility in the developer to become better.

[0158] The acid value of the (A1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20–200 mg KOH / g, more preferably 60–150 mg KOH / g, further preferably 80–130 mg KOH / g, and even more preferably 100–130 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting it to the upper limit or below, there is a tendency for better residual film yield.

[0159] The following are specific examples of (A1-I) epoxy (meth)acrylate resins. It should be noted that * in the examples indicates a bond.

[0160] [Chemical Formula 13]

[0161]

[0162] [Chemical Formula 14]

[0163]

[0164] [Chemical Formula 15]

[0165]

[0166] [Chemical Formula 16]

[0167]

[0168] <(A1-II) Epoxy (Meth)acrylate Resins>

[0169] [Chemical Formula 17]

[0170]

[0171] In formula (A1-II), R 13 Each can independently represent a hydrogen atom or a methyl group, R 14 R represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following groups independently represents a divalent aliphatic group that may optionally have substituents; m and n each independently represent integers from 0 to 2; and * represents a bond.

[0172] From the viewpoint of luminescence properties, a structure having formula (A1-II) is preferred.

[0173] (R 14 )

[0174] In formula (A1-II), R 14 This indicates a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain.

[0175] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0176] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, there is a tendency to obtain a robust film more easily and to avoid surface roughness during development. By setting it to the upper limit or below, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0177] 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. Furthermore, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting it to the lower limit or above, there is a tendency to obtain a robust film more easily and to avoid surface roughness during development. By setting it to the upper limit or below, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0178] Examples of aliphatic rings among aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of residual film yield and resolution, the adamantane ring is preferred.

[0179] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 4, and even more preferably 2 to 4, particularly preferably 3 to 4. By setting the value above the lower limit, there is a tendency to obtain a robust film more easily and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0180] Aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. Furthermore, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 6 to 40, further preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15. By setting the value above the lower limit, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency for patterning characteristics to become better.

[0181] Examples of aromatic rings in aromatic cyclic groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, and benzo[a]pyrene rings. Cyclic rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings. From the viewpoint of patterning properties, fluorene rings are preferred.

[0182] The divalent hydrocarbon group in a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. Examples include divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0183] Divalent aliphatic groups can be categorized as linear, branched, or cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred; conversely, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. 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. Furthermore, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 25 is preferred, more preferably 3 to 20, and even more preferably 6 to 15. By setting the value above the lower limit, there is a tendency to obtain a robust film, reduce surface roughness during development, and improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve high residual film rate after development, and improve resolution.

[0184] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeletal rigidity, methylene is preferred.

[0185] Examples of divalent branched aliphatic groups include those having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl as side chains.

[0186] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to produce a robust film and improve substrate adhesion. Furthermore, by setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0187] Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoborane, and adamantane rings. From the viewpoint of skeletal rigidity, groups obtained by removing two hydrogen atoms from adamantane rings are preferred.

[0188] Substituents that can be optionally present as divalent aliphatic groups include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0189] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Furthermore, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the value above the lower limit, there is a tendency to obtain a robust film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0190] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon ring group can be a monocyclic or fused ring. Examples of divalent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, which have two free valences. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0191] Aromatic heterocycles, as divalent aromatic heterocyclic groups, can be monocyclic or fused rings. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazolium rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazolium rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolinium rings, quinoxaline rings, phenanthridine rings, naphthalene-intercalated diazabenzene rings, quinazoline rings, quinazolineone rings, and azurite rings. From the viewpoint of patterning properties, benzene rings or naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0192] Substituents optionally present in the divalent aromatic cyclic group include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of developing solubility, unsubstituted groups are preferred.

[0193] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0194] 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. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to obtain a strong film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0195] The number of divalent aromatic ring 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. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to obtain a robust film, to reduce surface roughness during development, and to improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, to achieve a high residual film rate after development, and to improve resolution.

[0196] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups, examples include groups represented by the above formulas (A1-IA) to (A1-IF). From the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane, groups represented by formula (A1-IC) are preferred.

[0197] There are no particular limitations on the bonding mode of the cyclic hydrocarbon group as a side chain, relative to these divalent hydrocarbon groups. For example, the cyclic hydrocarbon group as a side chain can be formed by replacing one hydrogen atom of the aliphatic group or the aromatic cyclic group with a cyclic hydrocarbon group as a side chain, or by including one carbon atom of the aliphatic group to form a cyclic hydrocarbon group as a side chain.

[0198] (R 15 R 16 )

[0199] In formula (A1-II), R 15 and R 16 Each independently represents a divalent aliphatic group that optionally has substituents.

[0200] Divalent aliphatic groups can be categorized as linear, branched, or cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred; conversely, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. 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. Furthermore, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, more preferably 3 to 15, and even more preferably 6 to 10. By setting the value above the lower limit, there is a tendency to obtain a robust film, reduce surface roughness during development, and improve adhesion to the substrate. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve high residual film rate after development, and improve resolution.

[0201] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. From the viewpoint of skeletal rigidity, methylene is preferred.

[0202] Examples of divalent branched aliphatic groups include those with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains.

[0203] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 12 or less, more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, more preferably 2 to 10. By setting the value above the lower limit, there is a tendency to produce a robust film and improve substrate adhesion. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve high residual film rate after development, and improve resolution.

[0204] Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, and dicyclopentadiene rings. From the viewpoint of skeletal rigidity, groups obtained by removing two hydrogen atoms from dicyclopentadiene or adamantane rings are preferred.

[0205] Substituents that can be optionally present as divalent aliphatic groups include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0206] (m, n)

[0207] In formula (A1-II), m and n each independently represent integers from 0 to 2. By setting them to the lower limit or higher, there is a tendency for pattern adaptability to improve and for surface roughness to be less likely to occur during development. Furthermore, by setting them to the upper limit or lower, there is a tendency for developability to improve. From the viewpoint of developability, it is preferable that m and n are 0. From the viewpoint of pattern adaptability and suppressing surface roughness during development, it is preferable that m and n are 1 or higher.

[0208] From the viewpoint of the adhesion to the substrate, the partial structure represented by formula (A1-II) is preferably the partial structure represented by the following general formula (A1-II-1).

[0209] [Chemical Formula 18]

[0210]

[0211] In formula (A1-II-1), R 13 R 15 R 16 , m and n have the same meaning as in equation (A1-II), R α The symbol represents a monovalent cyclic hydrocarbon group optionally having substituents, p represents an integer greater than 1, and * represents a bond. The benzene ring in formula (A1-II-1) can be further substituted with any substituents.

[0212] (R α )

[0213] In formula (A1-II-1), R α This indicates a monovalent cyclic hydrocarbon group that may optionally have substituents.

[0214] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0215] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 6 is preferred, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the value above the lower limit, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency for patterning characteristics to become better.

[0216] 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. Furthermore, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting it to the lower limit or above, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting it to the upper limit or below, there is a tendency for patterning characteristics to become better.

[0217] Examples of aliphatic rings among aliphatic cyclic groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of robust film properties, the adamantane ring is preferred.

[0218] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Furthermore, it is preferably 10 or less, and even more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting the value above the lower limit, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency for patterning characteristics to become better.

[0219] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Additionally, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the value above the lower limit, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency for patterning characteristics to become better.

[0220] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of developing solubility, fluorene rings are preferred.

[0221] Substituents optionally present in the cyclic hydrocarbon group include, for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0222] p represents an integer greater than or equal to 1, preferably greater than or equal to 2. Furthermore, it is preferably less than or equal to 3. For example, it is preferably 1 to 3, more preferably 2 to 3. By setting it to the lower limit or above, there is a tendency for the film curing degree and residual film rate to become better. By setting it to the upper limit or below, there is a tendency for the developability to become better.

[0223] From the perspective of robust film curing, R α Preferably, it is a monovalent aliphatic cyclic group, and more preferably, it is an adamantyl group.

[0224] The benzene ring in formula (A1-II-1) can be further substituted with any substituents. Examples of substituents include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more.

[0225] From the perspective of patterning characteristics, unsubstituted is preferred.

[0226] The following are specific examples of some structures represented by equation (A1-II-1).

[0227] In the following examples, * represents a bond.

[0228] [Chemical Formula 19]

[0229]

[0230] [Chemical Formula 20]

[0231]

[0232] [Chemical Formula 21]

[0233]

[0234] [Chemical Formula 22]

[0235]

[0236] [Chemical Formula 23]

[0237]

[0238] From the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane, the partial structure represented by formula (A1-II) is preferably represented by the following general formula (A1-II-2).

[0239] [Chemical Formula 24]

[0240]

[0241] In formula (A1-II-2), R 13 R 15 R 16 , m and n have the same meaning as in equation (A1-II), R β * indicates a divalent cyclic hydrocarbon group that may optionally have substituents, and * indicates a bonded bond.

[0242] The benzene ring in formula (A1-II-2) can be further substituted with any substituents.

[0243] (R β )

[0244] In formula (A1-II-2), R β This indicates a divalent cyclic hydrocarbon group that may optionally have substituents.

[0245] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0246] The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 2 to 5. By setting the value above the lower limit, there is a tendency to obtain a robust film more easily and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency to suppress sensitivity degradation, achieve a high residual film rate after development, and improve resolution.

[0247] The aliphatic cyclic group preferably has 4 or more carbon atoms, more preferably 6 or more, and even more preferably 8 or more. Furthermore, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 6 to 35, and even more preferably 8 to 30. By setting it to the lower limit or above, there is a tendency to suppress roughness of the film surface during development. By setting it to the upper limit or below, there is a tendency to suppress the deterioration of sensitivity, achieve a high residual film rate after development, and improve resolution.

[0248] Examples of aliphatic rings that can be used as aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of residual film yield and resolution after development, the adamantane ring is preferred.

[0249] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5. By setting it to the lower limit or above, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting it to the upper limit or below, there is a tendency to easily suppress sensitivity degradation or film reduction and improve resolution.

[0250] As aromatic cyclic groups, examples include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups.

[0251] The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and even more preferably 10 or more. Furthermore, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15. By setting it to the lower limit or above, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting it to the upper limit or below, there is a tendency to easily suppress sensitivity degradation or film reduction and improve resolution.

[0252] Examples of aromatic rings in aromatic ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the perspective of residual film yield, fluorene rings are preferred. It is speculated that because the plane forming the fluorene ring is orthogonal to the bonds connecting the two benzene rings, its volume increases, resulting in a more rigid framework that is less prone to developer penetration and shrinkage during firing, thus leading to a higher residual film yield.

[0253] Substituents optionally present in the cyclic hydrocarbon group include, for example, alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0254] From the perspective of reducing film thickness and improving resolution, R β Preferably, it is a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group. From the viewpoint of patterning properties, R β Preferably, it is a divalent aromatic cyclic group, and more preferably a divalent fluorene cyclic group.

[0255] The benzene ring in formula (A1-II-2) can be further substituted with any substituents. Examples of substituents include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more.

[0256] Furthermore, the two benzene rings can be linked via substituents. Examples of substituents in this case include divalent groups such as -O-, -S-, -NH-, and -CH2-.

[0257] From the viewpoint of patterning properties, unsubstituted is preferred. Furthermore, from the viewpoint of minimizing film loss, methyl-substituted is preferred.

[0258] Below are specific examples of some structures represented by equation (A1-II-2). It should be noted that * in the examples represents bonding bonds.

[0259] [Chemical Formula 25]

[0260]

[0261] [Chemical Formula 26]

[0262]

[0263] [Chemical Formula 27]

[0264]

[0265] [Chemical Formula 28]

[0266]

[0267] From the viewpoint of coating residual film rate and patterning characteristics, the partial structure represented by formula (A1-II) is preferably the partial structure represented by the following general formula (A1-II-3).

[0268] [Chemical Formula 29]

[0269]

[0270] In formula (A1-II-3), R 13 R 14 R 15 R 16 , m and n have the same meaning as in equation (A1-II), R Z It represents a hydrogen atom or a polyacid residue.

[0271] A polybasic acid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. It should be noted that it is also possible to further remove one more OH group, which then combines with the R group in other molecules represented by formula (A1-II-3). Z Shared. That is, multiple formulas (A1-II-3) can be shared via R. Z And links.

[0272] Examples of polycarboxylic acids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

[0273] From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyl tetracarboxylic acid are preferred, and tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and biphenyl tetracarboxylic acid are more preferred.

[0274] (A1-II) An epoxy (meth)acrylate resin molecule may contain one or more of the structures represented by formula (A1-II-3), for example, R Z Partial structure of hydrogen atom and R Z The partial structures of polybasic acid residues can coexist.

[0275] The number of partial structures represented by formula (A1-II) contained in one molecule of an epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Furthermore, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10. By setting the value above the lower limit, there is a tendency to easily obtain a robust film and to avoid surface roughness during development. By setting the value below the upper limit, there is a tendency to easily suppress sensitivity degradation or film reduction and improve resolution.

[0276] The weight-average molecular weight (Mw) of the (A1-II) epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC) and converted to polystyrene, is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Furthermore, it is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 10000, more preferably 1500 to 10000, further preferably 1500 to 8000, even more preferably 2000 to 8000, and particularly preferably 2000 to 7000. By setting it to the lower limit or above, there is a tendency for a better residual film yield. By setting it to the upper limit or below, there is a tendency for better solubility in the developer.

[0277] The acid value of the (A1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20–200 mg KOH / g, more preferably 60–150 mg KOH / g, further preferably 80–130 mg KOH / g, and even more preferably 100–130 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting it to the upper limit or below, there is a tendency for better residual film yield.

[0278] (A1) Epoxy (meth)acrylate resins can be used alone or in combination with two or more resins.

[0279] <(A2) Resins containing isocyanuric acid backbone>

[0280] The photosensitive resin composition of the present invention can use a resin containing an isocyanuric acid backbone having olefinic double bonds and carboxyl groups. (Hereinafter referred to simply as (A2) resin containing an isocyanuric acid backbone)

[0281] By incorporating an isocyanuric acid skeleton, olefinic double bonds, and carboxyl groups, the chemical resistance and heat resistance are improved, and the amount of decomposition products during development and firing processes is reduced. As a result, there is a tendency for the current density to increase when a voltage is applied in the organic electro-electronic element.

[0282] (A2) Resins containing isocyanuric acid skeletons are (A) alkali-soluble resins. There are no particular limitations as long as they have olefinic double bonds, carboxyl groups and isocyanuric acid skeletons. For example, the following resins (A2-1) and (A2-2) can be listed.

[0283] (A2-1) A resin obtained by further reacting a compound containing an epoxy group with an isocyanuric acid skeleton and an α,β-unsaturated monocarboxylic acid and / or ester compound with a polybasic acid and / or its anhydride.

[0284] Examples of epoxy-containing compounds having an isocyanuric acid skeleton include compounds represented by the following general formula (A2-1-1).

[0285] [Chemical Formula 30]

[0286]

[0287] In equation (A2-1-1), R 4 ~R 6 Each can be independently represented as an alkylene group, which may be truncated midway by an ether-like oxygen atom.

[0288] As an alkylene group, it is preferred to have 1 or more carbon atoms. Furthermore, it is preferred to have 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 2 or fewer. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 6 carbon atoms are preferred, more preferably 1 to 4, and even more preferably 1 to 2. The alkylene group can be linear or branched. By setting it below the aforementioned upper limit value, there is a tendency for improved developability and gas barrier properties.

[0289] Examples of alkylene groups include: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, and ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene, which are truncated by an ether-like oxygen atom. From the viewpoint of gas barrier properties, methylene, ethylene, and n-propylene are preferred, and methylene is more preferred.

[0290] Examples of α,β-unsaturated monocarboxylic acids and / or ester compounds include: (meth)acrylic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substitutions at the α-position of (meth)acrylic acid; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyl... Monomers obtained by adding oxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid; or by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl methacrylate or pentaerythritol tri(meth)acrylate. From a sensitivity perspective, (meth)acrylic acid is preferred.

[0291] As a method for adding α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups to epoxy resins, the same method as that used for (A1) epoxy (meth)acrylate resins can be used.

[0292] Examples of polybasic acids and / or their anhydrides include, for example: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and their anhydrides.

[0293] Succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyl tetracarboxylic acid, and their anhydrides are preferred. Pyromellitic acid and its anhydrides are particularly preferred.

[0294] The addition reaction of polybasic acids and / or their anhydrides can be carried out using the same method as that used for (A1) epoxy (meth)acrylate resins.

[0295] As α,β-unsaturated monocarboxylic acids and / or ester compounds, compounds identical to those described in the section on (A1) epoxy (meth)acrylate resins can be listed.

[0296] (A2-2) A resin obtained by reacting a polyisocyanate compound having an isocyanuric acid backbone with an acid or anhydride, and then reacting the resulting compound with an epoxy-containing (meth)acrylate compound.

[0297] As for the resin in (A2-2), examples include the resin and its intermediates described in Japanese Patent Application Publication No. 2020-75994.

[0298] (A2) The weight-average molecular weight (Mw) of the resin containing the isocyanurate backbone is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Furthermore, it is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7000 or less. The above upper and lower limits can be combined arbitrarily.

[0299] For example, a value of 1000 to 10000 is preferred, more preferably 1500 to 10000, further preferably 1500 to 8000, even more preferably 2000 to 8000, and particularly preferably 2000 to 7000. By setting the value above the lower limit, there is a tendency to suppress excessive solubility in the developer. By setting the value below the upper limit, there is a tendency to achieve good solubility in the developer.

[0300] (A2) The acid value of the resin containing the isocyanuric acid backbone is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 20 to 200 mg KOH / g, more preferably 60 to 150 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting it to the upper limit or below, there is a tendency for better residual film yield.

[0301] <(A3) Acrylic Copolymer Resin>

[0302] From the viewpoint of compatibility with pigments, dispersants, etc., (A3) acrylic copolymer resin can be used as the (A3) acrylic copolymer resin. For example, the acrylic copolymer resin described in Japanese Patent Application Publication No. 2014-137466 can be preferred as the (A3) acrylic copolymer resin.

[0303] As an (A3) acrylic copolymer resin, examples include copolymers of an olefinic unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (A3-1)") with other copolymerizable olefinic unsaturated monomers (hereinafter referred to as "unsaturated monomer (A3-2)").

[0304] Examples of unsaturated monomers (A3-1) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesocarboxylic acid; mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids with two or more tertiary groups such as succinate mono[2-(meth)acryloyloxyethyl] ester and phthalate mono[2-(meth)acryloyloxyethyl] ester; mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends such as ω-carboxylated polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0305] These unsaturated monomers (A3-1) can be used alone or in combination of two or more.

[0306] Examples of unsaturated monomers (A3-2) include: N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene.

[0307] Methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl methacrylate, isobornyl methacrylate, tricyclohexyl methacrylate [5.2.1.0] 2,6 Decane-8-ester, dicyclopentenyl (meth)acrylate, glyceryl mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc. (meth)acrylates;

[0308] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0] 2,6Vinyl ethers such as decane-8-yl vinyl ether, pentacyclic pentadecyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane;

[0309] Polystyrene, poly(methyl methacrylate), poly(n-butyl methacrylate), polysiloxane, and other macromonomers have mono(meth)acryloyl groups at the ends of their polymer molecular chains.

[0310] These unsaturated monomers (A3-2) can be used alone or in combination of two or more.

[0311] In the copolymer of unsaturated monomer (A3-1) and unsaturated monomer (A3-2), the copolymerization ratio of unsaturated monomer (A3-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (A3-1) within such a range, there is a tendency to obtain a photosensitive resin composition with excellent alkali developability and storage stability.

[0312] Examples of copolymers of unsaturated monomer (A3-1) and unsaturated monomer (A3-2) include those disclosed in Japanese Patent Application Publication Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.

[0313] The copolymer of unsaturated monomer (A3-1) and unsaturated monomer (A3-2) can be manufactured by known methods, for example, by methods disclosed in Japanese Patent Application Publication No. 2003-222717, Japanese Patent Application Publication No. 2006-259680, and International Patent Application Publication No. 2007 / 029871, which control its structure, Mw, and Mw / Mn (Mn is the number average molecular weight).

[0314] In addition to the above, the resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 may also be used as (A3) acrylic copolymer resin.

[0315] <(B) Photopolymerization initiators>

[0316] The photopolymerization initiator (B) used in this invention is a component that directly absorbs light, induces a decomposition reaction or a hydrogen abstraction reaction, and generates polymerization-active free radicals. Additives such as polymerization accelerators (chain transfer agents) and sensitizing pigments can be added as needed.

[0317] Examples of photopolymerization initiators (B) include: metallocene compounds containing dititanium compounds as described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyltriazine derivatives as described in Japanese Patent Application Publication No. 10-39503; α-aminoalkyl phenyl ketone derivatives; and oxime ester compounds as described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0318] Examples of metallocene compounds include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,4,6-trifluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,6-difluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,4-difluorobenzene-1-yl) titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl) titanium, bis(methylcyclopentadienyl)bis(2,6-difluorobenzene-1-yl) titanium, and dicyclopentadienyl[2,6-di-fluoro-3-(pyrrolo-1-yl)-phenyl-1-yl] titanium.

[0319] Examples of hexaaryl biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0320] Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6”-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0321] Examples of halomethyltriazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine.

[0322] Examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0323] As photopolymerization initiators (B), oxime ester compounds are effective, particularly considering sensitivity and printability. For example, such highly sensitive oxime ester compounds are especially useful when using alkali-soluble resins containing phenolic hydroxyl groups. Due to their high quantum yield in the photoreaction and the high reactivity of the generated free radicals, oxime ester compounds can achieve high sensitivity with small quantities and are stable to thermal reactions, thus providing highly sensitive photosensitive resin compositions with minimal input.

[0324] Examples of oxime ester compounds include those represented by the following general formula (IV).

[0325] [Chemical Formula 31]

[0326]

[0327] In equation (IV), R 21a The group represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic cycloal group optionally having a substituent.

[0328] R 21b This indicates any substituent containing an aromatic ring.

[0329] R 22a This indicates an alkyl acyl group that may optionally have a substituent or an aromatic acyl group that may optionally have a substituent.

[0330] n represents an integer that is either 0 or 1.

[0331] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in the solvent, it is preferably 1 or more, more preferably 2 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl.

[0332] Substituents optionally present in the alkyl group include, for example, aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0333] As R 21a The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is not particularly limited, but from the viewpoint of solubility in the photosensitive resin composition, 5 or more is preferred. Furthermore, from the viewpoint of developability, 30 or less is preferred, more preferably 20 or less, and even more preferably 12 or less. For example, 5 to 30 is preferred, more preferably 5 to 20, and even more preferably 5 to 12.

[0334] Examples of aromatic cyclic groups include phenyl, naphthyl, pyridyl, and furanyl. From the viewpoint of reproducibility, phenyl or naphthyl is preferred, and phenyl is more preferred.

[0335] Substituents optionally present in the aromatic cyclic group include, for example, hydroxyl, carboxyl, halogen, amino, amide, alkyl, alkoxy, and groups formed by linking these substituents. From the viewpoint of reproducibility, alkyl, alkoxy, and groups formed by linking them are preferred, and linked alkoxy groups are more preferred.

[0336] From a radiometric point of view, R 21a Preferably, it is an aromatic cyclic group having substituents, and more preferably, it is an aromatic cyclic group having an alkoxy group linked in the substituents.

[0337] As R 21b Examples of substituted carbazole groups, optionally substituted thioxanone groups, optionally substituted diphenyl sulfide groups, optionally substituted fluorenyl groups, or optionally substituted indole groups may be included. From the viewpoint of sensitivity, optionally substituted carbazole groups are preferred. From the viewpoint of electrical reliability, optionally substituted diphenyl sulfide groups are preferred.

[0338] R 22a The number of carbon atoms in the alkyl acyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is preferably 2 or more, more preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. Examples of alkyl acyl groups include acetyl, propionyl, and butyryl.

[0339] Substituents that may be optionally present on the alkyl acyl group include, for example, aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0340] R 22a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is preferably 7 or more, more preferably 8 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Examples of aryl groups include benzoyl and naphthyl.

[0341] Substituents that may be optionally present in the aryl group include, for example, hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0342] From a sensitivity perspective, R is preferred. 22a The alkanoyl group is optionally substituted, more preferably unsubstituted, and even more preferably acetyl.

[0343] For example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0344] From the perspective of reducing pollution caused by colorants, the photopolymerization initiator described in Japanese Patent Application Publication No. 2016-133574 may also be preferred.

[0345] Photopolymerization initiators can be used alone or in combination with two or more.

[0346] To improve sensing sensitivity, sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source can be incorporated into the photopolymerization initiator as needed. Examples of sensitizing pigments include: xanthones as described in Japanese Patent Application Publication Nos. 4-221958 and 4-219756; heterocyclic coumarin pigments as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; 3-coumarinone compounds as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; pyrrole methylene pigments as described in Japanese Patent Application Publication Nos. 6-19240; and Japanese Patent Application Publication Nos. 47-2528 and 54-15529. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publication No. 2, Japanese Published Publication No. 45-37377, Japanese Published Publication No. 48-84183, Japanese Published Publication No. 52-112681, Japanese Published Publication No. 58-15503, Japanese Published Publication No. 60-88005, Japanese Published Publication No. 59-56403, Japanese Published Publication No. 2-69, Japanese Published Publication No. 57-168088, Japanese Published Publication No. 5-107761, Japanese Published Publication No. 5-210240, and Japanese Published Publication No. 4-288818.

[0347] As sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino group and a phenyl group within the same molecule are more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are preferred; benzophenone compounds such as 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole are preferred. Compounds containing p-dialkylaminophenyl, such as 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc., are particularly preferred to be 4,4'-dialkylaminobenzophenone.

[0348] Sensitizing pigments can be used alone or in combination with two or more.

[0349] As polymerization accelerators, examples of aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminoacetophenone, as well as aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used. A polymerization accelerator can be used alone or in combination with two or more.

[0350] <(C) olefinic unsaturated compounds>

[0351] The photosensitive resin composition of the present invention contains (C) olefinic unsaturated compounds represented by the following general formula (2).

[0352] [Chemical Formula 32]

[0353]

[0354] (In equation (2), R) 4 ~R 6 Each independently represents an alkylene group, which is optionally truncated midway by an ether-like oxygen atom. R 7 ~R 9 Each can independently represent a hydrogen atom or a methyl group.

[0355] (C) The olefinic unsaturated compound has an isocyanuric acid ring skeleton, therefore, the photosensitive resin composition of the present invention tends to have higher developability and a smaller cone angle. Furthermore, it has a (meth)acryloyloxy group, therefore, the photosensitive resin composition of the present invention tends to have higher exposure sensitivity and a higher residual film rate. Further, it has a hydroxyl group, therefore, the boiling point tends to increase and the amount of gas (smoke) generated during the firing process of the photosensitive resin composition of the present invention tends to decrease. If an acid anhydride is added to the hydroxyl group, there is a tendency to easily cause the decomposition of the acid anhydride and increase smoke. Furthermore, the increase in carboxyl groups tends to decrease developability.

[0356] The smaller cone angle allows for more uniform deposition of organic materials when using spacers formed by curing photosensitive resin compositions to create organic electroluminescent elements. This reduces the likelihood of wire breakage and improves element productivity. A higher residual film rate prevents the tendency for decomposition products, byproducts, and uncured materials from the composition to remain or re-adhere to the anode. Less smoke reduces the amount of decomposition products adhering to and contaminating the chamber walls.

[0357] The presence of hydroxyl groups in three side chains results in a higher boiling point compared to compounds with one or two hydroxyl groups, leading to higher boiling points of thermal decomposition products during firing and reduced smoke production. Furthermore, the presence of (meth)acryloyloxy groups in three side chains also results in higher exposure sensitivity and less smoke.

[0358] As R 4 ~R 6 The alkylene group in the alkylene group preferably has 1 or more carbon atoms. Furthermore, it is preferable to have 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 2 or fewer. The alkylene group can be linear or branched. By setting it to the upper limit or below, there is a tendency for improved photosensitivity and a smaller cone angle.

[0359] Examples of alkylene compounds include: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, and ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene, which are truncated by an ether-type oxygen atom midway. From a printing plate-making point of view, methylene, ethylene, and n-propylene are preferred, and methylene is more preferred.

[0360] (C) The molecular weight of the olefinic unsaturated compound is not particularly limited, but is preferably 500 or more. Furthermore, it is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 500 to 1000, more preferably 500 to 800, and even more preferably 500 to 600. By setting it to the lower limit or above, there is a tendency for a higher boiling point and suppressed fumes. By setting it to the upper limit or below, there is a tendency for increased exposure sensitivity and improved development resistance or residual film yield.

[0361] (C) The double bond equivalent of the olefinic unsaturated compound is not particularly limited, but is preferably 170 or more, more preferably 180 or more. Furthermore, it is preferably 240 or less, more preferably 220 or less, and even more preferably 200 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 170 to 240, more preferably 170 to 220, and even more preferably 180 to 200. By setting it above the lower limit, there is a tendency to suppress smoke. By setting it below the upper limit, there is a tendency to improve developability and residual film yield.

[0362] As (C) olefinic unsaturated compounds, for example, structures represented by the following formulas (C1-1) and (C1-4) to (C1-8) can be listed.

[0363] [Chemical Formula 33]

[0364]

[0365] [Chemical Formula 34]

[0366]

[0367] From the viewpoint of exposure sensitivity, the structure represented by formula (C1-1) is preferred as a (C) olefinic unsaturated compound.

[0368] (C) There are no particular limitations on the method of manufacturing olefinic unsaturated compounds. For example, they can be obtained by adding (meth)acrylic acid to an epoxy resin represented by the following formula (3).

[0369] [Chemical Formula 35]

[0370]

[0371] <(C2) Unsaturated olefins other than (C) olefins>

[0372] In this invention, it may contain (C2) olefinic unsaturated compounds other than (C) olefinic unsaturated compounds. (Hereinafter, it is sometimes referred to as "(C2) olefinic unsaturated compounds")

[0373] (C2) An olefinically unsaturated compound is a compound other than (C) olefinically unsaturated compounds that have at least one olefinically unsaturated group in the molecule. Specifically, examples include: (meth)acrylic acid, alkyl (meth)acrylates, acrylonitrile, styrene, carboxylic acids having one olefinically unsaturated bond, and monoesters of polyhydric or monohydric alcohols.

[0374] In this invention, when the compound contains (C2) olefin unsaturated compounds, it is particularly preferred to use polyfunctional olefin monomers having two or more olefin unsaturated groups in one molecule. The number of olefin unsaturated groups in the polyfunctional olefin monomer is not particularly limited, but is preferably two or more, more preferably four or more, even more preferably five or more, and preferably eight or less, even more preferably seven or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 2 to 8 is preferred, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7. By setting the value above the lower limit, there is a tendency to achieve high sensitivity. Furthermore, by setting the value below the upper limit, there is a tendency to increase solubility in solvents.

[0375] Examples of polyfunctional olefin monomers include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

[0376] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, and other acrylates of aliphatic polyhydroxy compounds; methacrylates in which these acrylates are replaced with methacrylates; itaconic acid esters in which these acrylates are replaced with itaconic acid esters; crotonic acid esters in which these acrylates are replaced with crotonic acid esters; and maleic acid esters in which these acrylates are replaced with maleic acid esters.

[0377] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and other acrylates and methacrylates of aromatic polyhydroxy compounds.

[0378] Esters, obtained through the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds, are not necessarily a single substance. Examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0379] Furthermore, examples of polyfunctional olefin monomers used in this invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reactants of polyepoxides with hydroxyl (meth)acrylates or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate.

[0380] Examples of urethane (meth)acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.); U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.); UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.); UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi Chemical Co., Ltd.).

[0381] From the viewpoint of curability, as (C2) olefinic unsaturated compounds, alkyl (meth)acrylates are preferred, such as urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate. Polyisocyanate compounds and hydroxyl-containing (meth)acrylates are more preferred.

[0382] They can be used individually or in combination with two or more.

[0383] <(D) Coloring agent>

[0384] The photosensitive resin composition of the present invention preferably contains a (D) colorant. By containing a (D) colorant, moderate light absorption can be obtained, and moderate light-blocking properties can be obtained, especially in the case of its use in forming light-blocking components such as spacers.

[0385] The colorant (D) in this invention preferably contains an organic black pigment (D-1).

[0386] By containing organic black pigment (D-1), there is a tendency for the insulation properties to become better.

[0387] Examples of organic black pigments (D-1) include perylene black pigments, aniline black pigments, and benzodifuranone black pigments.

[0388] Examples of perylene black pigments include: Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).

[0389] Examples of aniline-based black pigments include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).

[0390] From the viewpoints of opacity, dispersibility, developability, and luminescence properties, benzodifuranone-based black pigments are preferred as organic black pigments (D-1).

[0391] Among benzodifuranone-based black pigments, from the viewpoints of opacity, dispersibility, developability, and luminescence properties, it is preferable to use an organic black pigment (hereinafter, sometimes referred to as "organic black pigment represented by general formula (D-1-1)") comprising at least one of the following groups: a compound selected from the general formula (D-1-1) (hereinafter, sometimes referred to as "compound (D-1-1)"), a geometric isomer of compound (D-1-1), a salt of compound (D-1-1), and a salt of a geometric isomer of compound (D-1-1).

[0392] [Chemical Formula 36]

[0393]

[0394] In equation (D-1-1), R 611 and R 616 Each can independently represent a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R 612 R 613 R 614 R 615 R 617 R 618 R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, and R. 621 COOH, COOR 621 COO - CONH2, CONHR 621 CONR 621 R 622 CN, OH, OR 621 COCR 621 、OOCNH2、OOCNHR 621 OOCNR 621 R 622 NO2, NH2, NHR 621 NR 621 R 622 , NHCOR 622 NR 621 COR 622 N=CH2, N=CHR 621 N = CR 621 R 622 SH, SR 621 SOR 621 SO2R 621 SO3R 621 SO3H, SO3 - SO2NH2, SO2NHR 621 or SO2NR 621 R622 Choose freely R 612 and R 613 R 613 and R 614 R 614 and R 615 R 617 and R 618 R 618 and R 619 and R 619 and R 620 At least one combination of the groups is optionally directly bonded to each other or optionally bonded through an oxygen atom, a sulfur atom, NH or NR atom. 621 Bridges are bonded together; R 621 and R 622 Each can be independently represented as an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, a cycloalkenyl group with 3 to 12 carbon atoms, or an alkynyl group with 2 to 12 carbon atoms.

[0395] The geometric isomers of compound (D-1-1) have the following core structures (where substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[0396] [Chemical Formula 37]

[0397]

[0398] When compound (D-1-1) is anionic, it is preferable to use a salt formed by compensating its charge with any known suitable cation, such as a metal, organic, inorganic, or organometallic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Furthermore, when the geometric isomers of compound (D-1-1) are anionic, the same salt is preferred.

[0399] Among the substituents in formula (D-1-1) and their definitions, there is a tendency for increased hiding power; therefore, the following groups are preferred. This is because the following substituents are considered to have no absorption and will not affect the hue of the pigment.

[0400] R 612 R 614 R 615 R 617 R 619 and R 620 Each atom is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

[0401] R 613 and R 618Each of the following is preferably an independent hydrogen atom, NO2, OCH3, OC2H5, bromine atom, chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3 - Further preferred are hydrogen atoms or SO3H, with hydrogen atoms being particularly preferred.

[0402] R 611 and R 616 Each atom is preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom.

[0403] Preferred selection of free R 611 With R 616 R 612 With R 617 R 613 With R 618 R 614 With R 619 and R 615 With R 620 At least one combination in the group is the same, more preferably R 611 With R 616 Same, R 612 With R 617 Same, R 613 With R 618 Same, R 614 With R 619 Same, and R 615 With R 620 same.

[0404] Alkyl groups having 1 to 12 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, or dodecyl.

[0405] Cycloalkyl groups having 3 to 12 carbon atoms include, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcareyl, careyl, menthyl, norpinyl, pinyl, adamantane-1-yl or adamantane-2-yl.

[0406] Alkenes with 2 to 12 carbon atoms include, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, or dodecenyl.

[0407] Cycloalkenyl groups with 3 to 12 carbon atoms include, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthene-8-yl, 4(10)-thujene-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcarbapen-3-yl or camphenyl.

[0408] Examples of alkynyl groups with 2 to 12 carbon atoms include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-dodecyn-12-yl.

[0409] Halogen atoms can be, for example, fluorine, chlorine, bromine, or iodine atoms.

[0410] The organic black pigment represented by formula (D-1-1) is preferably an organic black pigment comprising at least one of the following groups: a compound selected from the general formula (D-1-2) shown below (hereinafter also referred to as "compound (D-1-2)") and a geometrical isomer of compound (D-1-2).

[0411] [Chemical Formula 38]

[0412]

[0413] As a compound (D-1-2), for example, the trade name Irgaphor (registered trademark) Black S 0100CF (manufactured by BASF) can be cited.

[0414] The organic black pigment is preferably used by dispersion using the dispersant, solvent, and method described later. Furthermore, if a sulfonic acid derivative of compound (D-1-1), particularly a sulfonic acid derivative of compound (D-1-2), is present during dispersion, dispersibility and shelf life are sometimes improved; therefore, the organic black pigment preferably contains these sulfonic acid derivatives.

[0415] The (D) colorant that can be used in the photosensitive resin composition of the present invention can be used in combination with colorants other than organic black pigment (D-1). There are no particular limitations on the colorants that can be used in combination; pigments or dyes can be used. From the viewpoint of durability, pigments are preferred.

[0416] For example, organic coloring pigments other than organic black pigments and inorganic pigments can be listed. Here, organic coloring pigments can be listed as follows: red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0417] From the viewpoint of suppressing ultraviolet absorption, achieving high curability, and easily controlling the shape of the cured product, organic coloring pigments are preferred.

[0418] Organic coloring pigments used in conjunction with organic black pigments can be used alone or in combination with two or more. In particular, it is further preferred to use combinations of organic coloring pigments that produce a near-black color when combined with organic black pigments.

[0419] The chemical structures of these organic coloring pigments are not particularly limited; examples include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Below, specific examples of usable pigments are indicated by pigment numbers. In the following examples such as "CI Pigment Red 2," "CI" represents the dye index number.

[0420] As red pigments, examples of CI pigments include 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 1 49, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 23 2, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. From the viewpoint of light-blocking and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferred, and CI Pigment Red 177, 209, 224, 254 are even more preferred. It should be noted that, considering dispersibility and light-blocking properties, CI Pigment Red 177, 254, and 272 are preferred. When the photosensitive resin composition is cured by ultraviolet light, a pigment with low ultraviolet absorption is preferred as the red pigment; from this perspective, CI Pigment Red 254 and 272 are even more preferred.

[0421] Examples of orange pigments include CI pigments Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. From the viewpoint of dispersibility and opacity, CI pigments Orange 13, 43, 64, and 72 are preferred. When the photosensitive resin composition is cured by ultraviolet light, pigments with low ultraviolet absorption are preferred as orange pigments; from this viewpoint, CI pigments Orange 64 and 72 are more preferred.

[0422] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. From the viewpoint of light-blocking properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI Pigment Blue 15:6 is even more preferred. It should be noted that, from the perspectives of dispersibility and light-blocking properties, CI Pigment Blue 15:6, 16, and 60 are preferred. When the photosensitive resin composition is cured by ultraviolet light, it is preferable to use a pigment with low ultraviolet absorption rate as the blue pigment. From this point of view, CI Pigment Blue 60 is more preferred.

[0423] Examples of purple pigments include CI pigments 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-blocking properties, CI pigments 19, 23, and 29 are preferred, and CI pigment 23 is even more preferred. It should be noted that CI pigments 23 and 29 are preferred from the perspectives of dispersibility and light-blocking properties. When the photosensitive resin composition is cured by ultraviolet light, a pigment with low ultraviolet absorption is preferred as the purple pigment; from this viewpoint, CI pigment 29 is more preferred.

[0424] Examples of green pigments include CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59. CI pigment green 7 and 36 are preferred examples.

[0425] Examples of yellow pigments include CI pigments Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 1 34, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Preferred examples include CI pigment yellows 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, with further preferred examples including CI pigment yellows 83, 138, 139, 150, and 180.

[0426] From the viewpoint of the light-blocking properties and shape control of the cured product, it is preferable to use at least one selected from the group consisting of red pigment, orange pigment, blue pigment and purple pigment.

[0427] From the viewpoint of the light-blocking properties and shape control of the cured product, it is preferable to contain at least one of the following pigments.

[0428] Red pigments: CI Pigment Red 177, 254, 272.

[0429] Orange pigments: CI pigments orange 43, 64, 72.

[0430] Blue pigment: CI pigment blue 15:6, 60.

[0431] Purple pigments: CI pigments purple 23 and 29.

[0432] In cases where two or more organic coloring pigments are used, the combination of organic coloring pigments is not particularly limited. From the viewpoint of light-blocking properties, it is preferable to contain at least one selected from the group consisting of red and orange pigments, and at least one selected from the group consisting of blue and purple pigments.

[0433] There are no particular limitations on the combination of colors. From the point of view of light blocking, for example, combinations of red and blue pigments, blue and orange pigments, and blue, orange and purple pigments can be listed.

[0434] On the other hand, from the viewpoint of higher opacity, inorganic black pigments are preferred as inorganic pigments.

[0435] Examples of inorganic black pigments include: carbon black, acetylene black, lampblack, bone black, graphite, iron black, cyanine black, and titanium black.

[0436] From the perspective of light-blocking properties and image characteristics, carbon black is the preferred choice. Examples of carbon black include the following.

[0437] Mitsubishi Chemical Corporation manufactures: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #9 60, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #315 0, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B.

[0438] Made by Degussa: Printex (registered trademark, same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, ColorBlack S170.

[0439] Cabot Corporation manufactures: Monarch (registered trademark, same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACKPEARLS 480, PEARLS 130, VULCAN (registered trademark, same below) XC72R, ELFTEX (registered trademark) -8.

[0440] Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN100 0. RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

[0441] Carbon black that has undergone acid treatment on its surface can be used. For example, the carbon black described in Japanese Patent No. 3674086 is preferred. Furthermore, resin-coated carbon black can be used. When resin-coated carbon black is used, it improves the adhesion to the glass substrate and reduces the volume resistivity. As a resin-coated carbon black, the carbon black described in Japanese Patent Application Publication No. 09-71733 is preferred, for example. Resin-coated carbon black is preferred from the perspectives of volume resistivity and dielectric constant.

[0442] These pigments are preferably dispersed in a manner where the average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.25 μm or less. Here, the average particle size is based on the number of pigment particles.

[0443] In the photosensitive resin composition of the present invention, the average particle size of the pigment is a value determined based on the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement is performed on a sufficiently diluted photosensitive resin composition (typically diluted to a pigment concentration of about 0.005 to 0.2% by mass; if a concentration is recommended by the measuring equipment, that concentration is used). The measurement is performed at 25°C.

[0444] In addition to the organic pigments and black pigments mentioned above, dyes can also be used. Examples of dyes that can be used as colorants include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene dyes.

[0445] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0446] Examples of anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0447] Examples of phthalocyanine dyes include CI Variant Blue 5.

[0448] Examples of quinone imine dyes include Basic Blue 3 and Basic Blue 9.

[0449] Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64.

[0450] Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0451] <(E) Dispersant>

[0452] To ensure the stability of quality, and in order to finely disperse and stabilize the dispersion of the (D) colorant, the photosensitive resin composition of the present invention may contain (E) dispersant.

[0453] As the (E) dispersant, a polymeric dispersant having functional groups is preferred. Furthermore, from the perspective of dispersion stability, polymeric dispersants having the following functional groups are preferred: carboxyl group; phosphate group; sulfonic acid group; or their salts; primary, secondary, or tertiary amino group; quaternary ammonium group; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. In particular, from the viewpoint that pigments can be dispersed with a small amount of dispersant, polymeric dispersants having the following basic functional groups are especially preferred: primary, secondary, or tertiary amino group; quaternary ammonium group; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine.

[0454] Examples of polymeric dispersants include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers with amino groups and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0455] Examples of such dispersants, listed by trade name, include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0456] Polymer dispersants can be used alone or in combination with two or more.

[0457] From the viewpoint of pigment dispersibility, (E) the dispersant preferably contains either or both of a urethane polymeric dispersant and an acrylic polymeric dispersant having functional groups, and particularly preferably contains an acrylic polymeric dispersant.

[0458] From the perspective of dispersibility and preservation, polymeric dispersants with basic functional groups and either or both of polyester bonds and polyether bonds are preferred.

[0459] As a urethane and acrylic polymeric dispersant, examples include the DISPERBYK-160~167, 182 series (all urethane), DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic) (all manufactured by BYK-Chemie).

[0460] The amine value of the polymeric dispersant with basic functional groups is not particularly limited, but is preferably 1 mg KOH / g or more, more preferably 10 mg KOH / g or more, further preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, and particularly preferably 50 mg KOH / g or more. Furthermore, it is preferably 140 mg KOH / g or less, more preferably 120 mg KOH / g or less, further preferably 100 mg KOH / g or less, even more preferably 90 mg KOH / g or less, and particularly preferably 80 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1–140 mg KOH / g, more preferably 10–120 mg KOH / g, further preferably 20–100 mg KOH / g, even more preferably 40–90 mg KOH / g, and particularly preferably 50–80 mg KOH / g. By setting it to the lower limit or above, there is a tendency for better dispersibility. By setting it below the aforementioned upper limit value, there is a tendency for the compatibility with (A) alkali-soluble resin to become better.

[0461] From a dispersibility viewpoint, acrylic dispersants are preferably AB or BAB block copolymers composed of A blocks having the aforementioned functional groups and B blocks not having the aforementioned functional groups. In this case, the A blocks may contain, in addition to partial structures derived from monomers containing unsaturated groups that include the aforementioned functional groups, partial structures derived from monomers containing unsaturated groups that do not include the aforementioned functional groups. These structures may be contained in the A blocks in any manner, either through random copolymerization or block copolymerization. The proportion of the partial structures in the A blocks that do not contain functional groups is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, even more preferably 10% by mass or less, and particularly preferably 0% by mass.

[0462] From a dispersibility point of view, the B block is preferably composed only of partial structures derived from monomers containing unsaturated groups that do not contain the aforementioned functional groups. A B block may contain partial structures derived from two or more monomers, and these structures may be contained in the B block in any manner of random copolymerization or block copolymerization.

[0463] AB or BAB block copolymers are prepared, for example, by the living polymerization method shown below.

[0464] Living polymerization methods include anionic living polymerization, cationic living polymerization, and free radical living polymerization. In anionic living polymerization, the active species for polymerization is anion, as illustrated by the following process.

[0465] [Chemical Formula 39]

[0466]

[0467] In the above process, Ar 1 Ar is a monovalent organic group. 2 To be with Ar 1 Different monovalent organic groups, M is a metal atom, and s and t are integers greater than or equal to 1.

[0468] In free radical living polymerization, the active species for polymerization are free radicals, as illustrated by the following process.

[0469] [Chemical Formula 40]

[0470]

[0471] In the above process, Ar 1 Ar is a monovalent organic group. 2 To be with Ar 1 Different monovalent organic groups, j and k are integers greater than or equal to 1, R a R is a hydrogen atom or a monovalent organic group. b To be with R a Different hydrogen atoms or monovalent organic groups.

[0472] In synthesizing this acrylic dispersant, the following methods can be used: Japanese Patent Application Publication No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. The known methods described in al, Polym.J.17,977(1985), 18,1037(1986), Koichi Uezu, Koichi Hatada, Polymer Processing, 36,366(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46,189(1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109,4737(1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43,300(1985), DY Sogoh, WR Hertler et al, Macromolecules, 20,1473(1987), etc.

[0473] The acrylic dispersant used in this invention can be an AB block copolymer or a BAB block copolymer. The A-block / B-block ratio of the copolymer is not particularly limited, but is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio). By setting it within this range, there is a tendency to easily ensure a balance between dispersibility and storage stability.

[0474] In this invention, the amount of quaternary ammonium groups in 1g of the AB block copolymer and BAB block copolymer is preferably 0.1 to 10 mmol. By setting it within this range, there is a tendency to easily ensure good dispersibility.

[0475] Such acrylic dispersants may contain amino groups. The amine value of the acrylic dispersant is preferably 1 mg KOH / g or more, more preferably 10 mg KOH / g or more, further preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, and particularly preferably 50 mg KOH / g or more. Furthermore, it is preferably 140 mg KOH / g or less, more preferably 120 mg KOH / g or less, further preferably 100 mg KOH / g or less, even more preferably 90 mg KOH / g or less, and particularly preferably 80 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1–140 mg KOH / g, more preferably 10–120 mg KOH / g, further preferably 20–100 mg KOH / g, even more preferably 40–90 mg KOH / g, and particularly preferably 50–80 mg KOH / g. By setting it to the lower limit or above, there is a tendency for the dispersibility to become better. By setting it below the aforementioned upper limit value, there is a tendency for the compatibility with (A) alkali-soluble resin to become better.

[0476] Here, the amine value of acrylic dispersants is expressed as the mass of KOH equivalent to the amount of alkali per 1g of solid component in the dispersant sample, excluding the solvent, and is determined by the following method.

[0477] Accurately weigh 0.5–1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titration apparatus equipped with a pH electrode, neutralize and titrate the solution with 0.1 mol / L HClO4 acetic acid solution. Take the inflection point of the pH titration curve as the titration endpoint and calculate the amine value using the following formula.

[0478] Amine value [mgKOH / g] = (561 × V) / (W × S) [where W: represents the amount of dispersant sample weighed [g], V: represents the titration volume at the titration endpoint [mL], and S: represents the concentration of solid components in the dispersant sample [mass %].]

[0479] The weight-average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. Furthermore, it is preferably 50000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 50000, more preferably 3000 to 50000, further preferably 4000 to 20000, and particularly preferably 5000 to 15000. By setting it to the lower limit or above, there is a tendency for better dispersibility; conversely, by setting it to the upper limit or below, there is a tendency for viscosity changes to be less likely.

[0480] As an acrylic dispersant, it is preferred to have tertiary amino and / or quaternary ammonium groups.

[0481] When an acrylic dispersant has a quaternary ammonium group as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium group is not particularly limited. From the viewpoint of dispersibility, it is preferred that the acrylic dispersant has a repeating unit represented by the following general formula (V) (hereinafter, sometimes referred to as "repeating unit (V)").

[0482] [Chemical Formula 41]

[0483]

[0484] In equation (V), R 31 ~R 33 Each of the following is independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 31 ~R 33 Two or more elements can be optionally bonded together to form a ring structure. 34 X is a hydrogen atom or a methyl group. X is a divalent linker, Y is a hydrogen atom or a methyl group. - To counteract anions.

[0485] R of equation (V) 31 ~R 33 The alkyl group optionally having substituents can be either straight-chain or branched. Furthermore, it may also contain cyclic structures such as cyclohexyl or cyclohexylmethyl. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 10 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. For example, it is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 2.

[0486] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, methyl, ethyl, propyl, and butyl being more preferred, and methyl and ethyl being even more preferred.

[0487] R of equation (V) 31 ~R 33 The number of carbon atoms in the aryl group, which optionally has substituents, is not particularly limited, but is preferably 6 or more, and more preferably 16 or less, and even more preferably 12 or less. For example, 6 to 16 is preferred, and more preferably 6 to 12. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being even more preferred.

[0488] R of equation (V) 31 ~R 33 The number of carbon atoms in the aralkyl group optionally having substituents is not particularly limited, but is preferably 7 or more, further preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. For example, 7 to 16 is preferred, more preferably 7 to 12, even more preferably 7 to 10, and particularly preferably 7 to 8. Examples of aralkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl being preferred, and phenylmethyl and phenylethyl being more preferred.

[0489] From a dispersion perspective, R is preferred. 31 ~R 33 Each is independently an alkyl or aralkyl group, more preferably R. 31 ~R 33 Each can be methyl or phenylmethyl independently.

[0490] Y in equation (V) - For example, Cl can be listed as follows: - ,Br - I - ClO4 - BF4 - CH3COO - PF - .

[0491] Alternatively, the following may be preferred: aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions, and aromatic carboxylic acid anions as described in International Publication No. 2018 / 079659; and alkyl sulfate anions and alkyl sulfonic acid anions as described in International Publication No. 2019 / 107020.

[0492] As Y - From the viewpoint of development method, Cl is preferred. - From the viewpoint of luminescent properties, alkyl sulfonic acid anions are preferred.

[0493] When a polymeric dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility and luminescence properties, it is preferable to have a repeating unit represented by the following general formula (VI) (hereinafter, sometimes referred to as "repeating unit (VI)").

[0494] [Chemical Formula 42]

[0495]

[0496] In equation (VI), R 35 and R 36 Each of the following is independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 35 and R 36 They can be optionally bonded together to form a ring structure. R 37 It represents a hydrogen atom or a methyl group. Z represents a divalent linker.

[0497] R as in equation (VI) 35 and R 36 The alkyl group optionally having a substituent may preferably be used as R in formula (V). 31 ~R 33 The groups shown are examples.

[0498] R as in equation (VI) 35 and R 36 The aryl group, optionally having substituents, can preferably be used as R in formula (V). 31 ~R 33 The groups shown are examples.

[0499] R as in equation (VI) 35 and R 36 The aralkyl group optionally having a substituent may preferably be used as R in formula (V). 31 ~R 33 The groups shown are examples.

[0500] From the perspective of dispersibility and luminescence properties, R is preferred. 35 and R 36 Alkyl groups, each optionally having a substituent, are more preferably methyl or ethyl.

[0501] R as in equation (V) 31 ~R 33 R of formula (VI)35 and R 36 The alkyl, aralkyl, or aryl groups may optionally have substituents, such as halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups.

[0502] X in formula (V) and Z in formula (VI) can be, for example, alkylene groups with 1 to 10 carbon atoms, aryl groups with 6 to 12 carbon atoms, and -CONH-R. 43 -base, -COOR 44 -Base (where R) 43 and R 44 It is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms, preferably -COO-R. 44 - group, more preferably -COO-C2H4- group.

[0503] From the viewpoint of dispersion, it is preferable to have repeating units (V), and further from the viewpoint of luminescence properties, it is preferable to have repeating units (V) and repeating units (VI).

[0504] The proportion of the repeating unit (V) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. Furthermore, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0505] The proportion of the repeating unit (VI) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and particularly preferably 20 mol% or more. Furthermore, it is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less.

[0506] From the viewpoint of improving compatibility with alkali-soluble resin components such as solvents and improving dispersion stability, acrylic dispersants preferably have repeating units represented by the following general formula (VII) (hereinafter, sometimes referred to as "repeating unit (VII)").

[0507] [Chemical Formula 43]

[0508]

[0509] In equation (VII), R 40 It is ethylene or propylene, R 41 R is an alkyl group that optionally has substituents.42 It can be a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0510] R in equation (VII) 41 The alkyl group optionally having substituents can be either straight-chain or branched. Furthermore, it may also contain cyclic structures such as cyclohexyl or cyclohexylmethyl. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred.

[0511] From the viewpoint of compatibility and dispersibility with alkali-soluble resin components such as solvents, n in formula (VII) is preferably 1 or more, more preferably 2 or more. Furthermore, it is preferably 10 or less, more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 2 to 5.

[0512] The proportion of the repeating unit (VII) in all repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more. Furthermore, it is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%. Within these ranges, there is a tendency to easily balance compatibility with alkali-soluble resin components such as solvents and dispersion stability.

[0513] From the viewpoint of improving the compatibility of the dispersant with alkali-soluble resin components such as solvents and improving dispersion stability, acrylic dispersants preferably have repeating units represented by the following general formula (VIII) (hereinafter, sometimes referred to as "repeating unit (VIII)").

[0514] [Chemical Formula 44]

[0515]

[0516] In equation (VIII), R 38 It can be an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. R 39 It can be a hydrogen atom or a methyl group.

[0517] R in equation (VIII) 38The alkyl group optionally having substituents can be either straight-chain or branched. Furthermore, it may also contain cyclic structures such as cyclohexyl or cyclohexylmethyl. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. Furthermore, it is preferably 10 or less, more preferably 8 or less. Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, and 2-ethylhexyl, more preferably methyl, ethyl, propyl, butyl, and 2-ethylhexyl.

[0518] R in equation (VIII) 38 The number of carbon atoms in the aryl group, which optionally has substituents, is not particularly limited, but is preferably 6 or more. Furthermore, it is preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, it is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0519] R in equation (VIII) 38 The number of carbon atoms in the aralkyl group optionally having substituents is not particularly limited, but is preferably 7 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. For example, 7 to 16 is preferred, more preferably 7 to 12, and even more preferably 7 to 10. Examples of aralkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, or phenylbutyl being preferred, and phenylmethyl or phenylethyl being more preferred.

[0520] From the perspective of solvent compatibility and dispersion stability, R 38 Preferably alkyl or aralkyl, more preferably methyl, ethyl, butyl, 2-ethylhexyl or phenylmethyl.

[0521] As R 38 The alkyl group may optionally have substituents, for example, halogen atoms and alkoxy groups. The aryl or aralkyl group may optionally have substituents, for example, chain-like alkyl groups, halogen atoms, and alkoxy groups. R 38 The chain-like alkyl groups shown include either straight-chain or branched-chain structures.

[0522] From a dispersibility perspective, the proportion of the repeating unit (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Furthermore, it is preferably 80 mol% or less, more preferably 70 mol% or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 30-80 mol%, more preferably 40-80 mol%, and even more preferably 50-70 mol%.

[0523] Acrylic dispersants may have repeating units other than repeating units (V), (VI), (VII), and (VIII). Examples of such repeating units include those derived from the following monomers: styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic glycidyl ether, and N-methacryloylmorpholine.

[0524] From the viewpoint of further improving dispersibility, acrylic dispersants are preferably block copolymers having A-blocks and B-blocks, wherein the A-blocks have repeating units (V) and (VI), and the B-blocks do not have repeating units (V) and (VI). The block copolymers are preferably AB block copolymers or BAB block copolymers. By introducing not only quaternary ammonium groups but also tertiary amine groups into the A-blocks, there is an unexpected tendency for a significant improvement in the dispersing ability of the dispersant. Furthermore, the B-blocks preferably have repeating units (VII), and more preferably have repeating units (VIII).

[0525] In block A, repeating units (V) and repeating units (VI) can be contained in any manner, either random copolymerization or block copolymerization. Furthermore, a block A may contain two or more types of repeating units (V) and repeating units (VI), in which case the repeating units can be contained in the block A in any manner, either random copolymerization or block copolymerization.

[0526] The A block may contain repeating units other than repeating units (V) and (VI). Examples of such repeating units include repeating units derived from the aforementioned (meth)acrylate monomers. The content of repeating units other than repeating units (V) and (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably the A block does not contain such repeating units.

[0527] The B block may contain repeating units other than repeating units (VII) and (VIII). Examples of such repeating units include those derived from the following monomers: styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; and monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic glycidyl ether, and N-methacryloylmorpholine. The proportion of repeating units other than repeating units (VII) and (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably, the B block does not contain such repeating units.

[0528] These acrylic dispersants can be used alone, or in combination of two or more.

[0529] <Other co-components of the photosensitive resin composition>

[0530] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may also be appropriately combined with additives such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors.

[0531] (1) Adhesion enhancer

[0532] To improve adhesion to the substrate, the photosensitive resin composition of the present invention may contain an adhesion enhancer. Preferably, the adhesion enhancer is a silane coupling agent or a phosphate-containing compound.

[0533] As a silane coupling agent, various silane coupling agents such as epoxy, (meth)acrylic, and amino can be used alone, or two or more can be used in combination.

[0534] Examples of silane coupling agents include: (meth)acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane; ureosilanes such as 3-ureopropyltriethoxysilane; and isocyanate silanes such as 3-isocyanatepropyltriethoxysilane. Epoxy silane coupling agents are particularly preferred.

[0535] As a phosphate-containing compound, it is preferred to be a phosphate ester containing (meth)acryloyl group, and more preferably a compound represented by the following general formula (g1), (g2) or (g3).

[0536] [Chemical Formula 45]

[0537]

[0538] In equations (g1), (g2), and (g3), R 51 Represents a hydrogen atom or a methyl group, where l and l' are integers from 1 to 10, and m is 1, 2, or 3.

[0539] These phosphate-containing compounds can be used alone or in combination with two or more.

[0540] (2) Surfactants

[0541] To improve coatability, the photosensitive resin composition of the present invention may contain a surfactant.

[0542] As surfactants, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Considering the low likelihood of adverse effects on various properties, nonionic surfactants are preferred; and considering coatability, fluorinated or silicone surfactants are more preferred.

[0543] Examples of such surfactants include: TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar), and FC4430 (manufactured by 3M).

[0544] Surfactants can be used alone or in combination with two or more.

[0545] (3) Pigment derivatives

[0546] To improve dispersibility and shelf life, the photosensitive resin composition of the present invention may contain pigment derivatives as dispersing aids.

[0547] Examples of pigment derivatives include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolineone, dioxazine, anthraquinone, indanthrene, perylene, pyrene, diketopyrrolopyrrole, and dioxazine derivatives, with phthalocyanine and quinophthalone derivatives being preferred.

[0548] Substituents used as pigment derivatives include, for example, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are directly or indirectly bonded to the pigment skeleton via, for example, alkyl, aryl, or heterocyclic groups, with sulfonic acid groups being preferred. Multiple substituents can be substituted onto a single pigment skeleton, or various types of substituents can be substituted.

[0549] Examples of pigment derivatives include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinoline ketone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. They can be used individually or in combination of two or more.

[0550] (4) Thiol compounds

[0551] In addition to acting as polymerization accelerators, thiol compounds can also be added to improve adhesion to the substrate.

[0552] Examples of thiol compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene glycol dithiopropionate, butylene glycol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butylene glycol dithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, ethylene glycol bis(3-mercaptobutyrate), and butylene glycol dithiopropionate. Heterocyclic thiol compounds and aliphatic polyfunctional thiol compounds include glycol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These various thiol compounds can be used alone or in combination of two or more.

[0553] (5) Polymerization inhibitors

[0554] From the viewpoint of controlling the shape of the cured product, the photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is believed that by containing a polymerization inhibitor, free radical polymerization of the underlayer of the coating film is hindered, thereby enabling control of the cone angle (the angle between the support and the cured product in the cross-section of the cured product).

[0555] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred. From the viewpoint of particularly excellent safety for human health, hydroquinone monomethyl ether and methyl hydroquinone are preferred.

[0556] A polymerization inhibitor can be used alone or in combination with two or more.

[0557] In the manufacture of (C) alkali-soluble resin, a polymerization inhibitor is sometimes included in the resin, which can be used as the polymerization inhibitor of the present invention. Alternatively, in the manufacture of photosensitive resin compositions, a polymerization inhibitor that is the same as or different from the polymerization inhibitor can be added to the resin.

[0558] When the photosensitive resin composition contains a polymerization inhibitor, its content is not particularly limited. Relative to the total solids content of the photosensitive resin composition, it is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and preferably 0.3% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.0005% to 0.3% by mass, more preferably 0.001% to 0.2% by mass, and even more preferably 0.01% to 0.1% by mass. By setting it above the lower limit, there is a tendency to control the shape of the cured product. By setting it below the upper limit, there is a tendency to maintain the desired sensitivity.

[0559] (6) Solvent

[0560] The photosensitive resin composition of the present invention preferably contains a solvent. By including a solvent, the colorant can be dispersed or dissolved in the solvent, and coating becomes easier.

[0561] The photosensitive resin composition of the present invention is used, for example, in a state in which (A) an alkali-soluble resin, (B) a photopolymerization initiator, (D) a colorant, (E) a dispersant, and various other materials as needed are dissolved or dispersed in a solvent. From the viewpoint of dispersibility and coatability, organic solvents are preferred.

[0562] From the viewpoint of coatability, organic solvents with a boiling point of 100–300°C are preferred, and those with a boiling point of 120–280°C are more preferred. It should be noted that the boiling point referred to here is the boiling point at a pressure of 1013.25 hPa; the same applies to boiling points in the following text.

[0563] Examples of such organic solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and diol monoalkyl ethers;

[0564] Dialkyl ethers of glycols, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0565] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and other diol alkyl ether acetates;

[0566] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0567] Alkyl acetates such as cyclohexanol acetate;

[0568] Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0569] Ketones such as acetone, methyl ethyl ketone, methyl pentyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentyl ketone;

[0570] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0571] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0572] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0573] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0574] Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, and other chain or cyclic esters;

[0575] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0576] Halogenated hydrocarbons such as butyl chloride and pentyl chloride;

[0577] Ether ketones such as methoxymethylpentanone;

[0578] Nitriles such as acetonitrile and benzonitrile.

[0579] Commercially available organic solvents include, for example: Mineral Spirit, Varsol#2, Apco#18 Solvent, Apco Thinner, Socal Solvent No.1 and No.2, Solvesso#150, ShellTS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellulose Solvent (“Cellosolve” is a registered trademark. The same applies hereinafter), Ethyl Cellulose Solvent, Ethyl Cellulose Solvent Acetate, Methyl Cellulose Solvent Acetate, and Diethylene Glycol Dimethyl Ether (diglyme) (all trade names).

[0580] These organic solvents can be used alone or in combination of two or more.

[0581] When using photolithography to form the spacer wall, the organic solvent preferably has a boiling point of 100 to 240°C, more preferably has a boiling point of 120 to 200°C, and even more preferably has a boiling point of 120 to 170°C.

[0582] Considering the good balance of coatability and surface tension, as well as the high solubility of the constituent components in the composition, glycol alkyl ether acetates are preferred.

[0583] Diol alkyl ether acetates can be used alone or in combination with two or more.

[0584] Diol alkyl ether acetates may be used alone, or other organic solvents may be used in combination. As the organic solvent used in combination, monoalkyl glycol ethers are preferred. From the viewpoint of the solubility of the constituent components in the composition, propylene glycol monomethyl ether is preferred.

[0585] Diol monoalkyl ethers are highly polar. When added in excessive amounts, they tend to cause pigment agglomeration and increased viscosity of the resulting photosensitive resin composition, resulting in decreased storage stability. Therefore, the ratio of diol monoalkyl ethers to the total mass of the solvent is preferably 5 to 30 by mass, more preferably 5 to 20 by mass.

[0586] By using organic solvents with boiling points of 150°C or higher (hereinafter sometimes referred to as "high-boiling solvents"), the photosensitive resin composition becomes difficult to dry. However, since high-boiling solvents can also be used because they prevent the uniform dispersion of pigments in the composition from being destroyed by rapid drying, they can also be used. For example, they have the effect of preventing the generation of foreign matter defects caused by the precipitation / curing of colorants at the tip of the slit nozzle. Considering the high effectiveness of such effects, when using high-boiling solvents, it is preferable to use diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, or diethylene glycol monoethyl ether acetate.

[0587] When using a high-boiling-point solvent, the content of the high-boiling-point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. By setting it to the lower limit or above, there is a tendency to suppress, for example, foreign matter defects caused by the precipitation / curing of colorants at the tip of the slit nozzle. By setting it to the upper limit or below, there is a tendency to suppress problems such as prolonged drying time of the composition, poor cycle time of the vacuum drying process, or pin marks from pre-baking.

[0588] The high-boiling-point solvent can be a glycol alkyl ether acetate, or alternatively, a glycol alkyl ether. In this case, it is also possible to omit the high-boiling-point solvent.

[0589] Preferred high-boiling-point solvents include, for example, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and glyceryl triacetate.

[0590] <Proportion of each component in the photosensitive resin composition>

[0591] The proportion of colorant (D) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total solids content of the photosensitive resin composition. Furthermore, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, even more preferably 15 to 30% by mass, even more preferably 15 to 25% by mass, and particularly preferably 15 to 20% by mass. By setting it above the lower limit, there is a tendency to ensure light-blocking properties. By setting it below the upper limit, there is a tendency to reduce the dispersion dose and suppress surface roughness.

[0592] The content of the organic black pigment (D-1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total solids content of the photosensitive resin composition. Furthermore, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, even more preferably 15 to 30% by mass, even more preferably 15 to 25% by mass, and particularly preferably 15 to 20% by mass. By setting it above the lower limit, there is a tendency to ensure light-blocking properties. By setting it below the upper limit, there is a tendency for the residual film rate to increase.

[0593] When the photosensitive resin composition of the present invention contains organic coloring pigments other than organic black pigment (D-1), the proportion of such pigments is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more in the total solids content of the photosensitive resin composition. Furthermore, it is preferably 30% by mass or less, more preferably 20% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and even more preferably 10 to 20% by mass. By setting it to the lower limit or above, there is a tendency to suppress the loss of ultraviolet light required for curing and to increase the light-blocking property. By setting it to the upper limit or below, there is a tendency to increase the residual film rate.

[0594] (E) The proportion of the dispersant is not particularly limited, but relative to the total solids content of the photosensitive resin composition, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 7% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 3 to 7% by mass. By setting it to the lower limit or above, there is a tendency to easily obtain sufficient dispersibility. By setting it to the upper limit or below, there is a tendency to reduce degassing.

[0595] The proportion of (E) dispersant relative to 100 parts by weight of (D) colorant is not particularly limited, but is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, even more preferably 15 parts by weight or more, and preferably 50 parts by weight or less, even more preferably 30 parts by weight or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 50 parts by weight is preferred, more preferably 10 to 50 parts by weight, and even more preferably 15 to 30 parts by weight. By setting the value above the lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting the value below the upper limit, there is a tendency for the residual film rate to increase.

[0596] (A) The proportion of alkali-soluble resin is not particularly limited, but relative to the total solids content of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, even more preferably 30 to 60% by mass, even more preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. By setting it to the lower limit or above, there is a tendency to suppress the decrease in solubility of the unexposed portion in the developer and to suppress poor development. By setting it to the upper limit or below, there is a tendency to maintain appropriate sensitivity and suppress the dissolution of the exposed portion caused by the developer and the reduction of the cone angle.

[0597] When the photosensitive resin composition of the present invention comprises an (A1) epoxy (meth)acrylate resin, the content ratio of the (A1) epoxy (meth)acrylate resin is not particularly limited. Relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 15 to 60% by mass, even more preferably 20 to 60% by mass, even more preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. By setting it to the lower limit or above, there is a tendency to ensure the solubility of the unexposed portion in the developer. By setting the value below the upper limit, there is a tendency to maintain appropriate sensitivity, suppress dissolution of the exposed part caused by the developer, and suppress the reduction in pattern clarity and adhesion.

[0598] When the (A) alkali-soluble resin includes an (A1) epoxy (meth)acrylate resin, the proportion of the (A1) epoxy (meth)acrylate resin in the (A) alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. Furthermore, it is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 20 to 100% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass. By setting it to the lower limit or above, there is a tendency to ensure the solubility of the unexposed portion in the developer. By setting it to the upper limit or below, there is a tendency to maintain appropriate sensitivity, suppress dissolution of the exposed portion caused by the developer, and suppress the reduction in pattern clarity and adhesion.

[0599] When the alkali-soluble resin (A) comprises the resin containing the isocyanurate backbone (A2), the proportion of the resin containing the isocyanurate backbone (A2) in the alkali-soluble resin (A) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 20 to 90% by mass is preferred, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass. By setting it to the lower limit or above, there is a tendency for improved luminescence properties. By setting it to the upper limit or below, there is a tendency for improved developability.

[0600] (B) The proportion of the photopolymerization initiator is not particularly limited, but relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, particularly preferably 6% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass. By setting it to the lower limit or above, there is a tendency to suppress the decrease in sensitivity. By setting it to the upper limit or below, there is a tendency to suppress the decrease in the solubility of the unexposed portion in the developer and suppress poor development.

[0601] When using a polymerization accelerator together with (B) the photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited. It is preferably 0.05% by mass or more relative to the total solids content of the photosensitive resin composition of the present invention, and more preferably 10% by mass or less, and more preferably 5% by mass or less. For example, it is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass. Furthermore, the polymerization accelerator is preferably used in a ratio of 0.1 to 50 parts by mass relative to 100 parts by mass of the (B) photopolymerization initiator, and more preferably 0.1 to 20 parts by mass. By setting the content ratio of the polymerization accelerator to the lower limit or above, there is a tendency to suppress the decrease in sensitivity to exposure light. By setting it to the upper limit or below, there is a tendency to suppress the decrease in the solubility of the unexposed portion in the developer and suppress poor development.

[0602] When the sensitized pigment is used together with the photopolymerization initiator (B), the content of the sensitized pigment is not particularly limited. From the viewpoint of sensitivity, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total solid content in the photosensitive resin composition.

[0603] The total content ratio of (C) olefinic unsaturated compounds to (C2) olefinic unsaturated compounds is not particularly limited. Relative to the total solids content of the photosensitive resin composition of the present invention, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 5 to 25% by mass, even more preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass. By setting it to the lower limit or above, there is a tendency to maintain appropriate sensitivity, suppress dissolution of the exposed portion caused by the developer, and suppress the reduction in pattern clarity and adhesion. By setting it to the upper limit or below, there is a tendency to suppress the increased penetration of the developer into the exposed portion and easily obtain good images.

[0604] (C) The proportion of the olefinic unsaturated compound is not particularly limited, but relative to the total solids content of the photosensitive resin composition, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass, and further preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, even more preferably 5 to 25% by mass, even more preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass. By setting it to the lower limit or above, there is a tendency to improve exposure sensitivity. By setting it to the upper limit or below, there is a tendency for good solubility in the developer.

[0605] The proportion of (C) olefinic unsaturated compounds is not particularly limited, but relative to the total amount of (C) olefinic unsaturated compounds and (C2) olefinic unsaturated compounds, it is preferably 4% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. Furthermore, it is preferably 100% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 4 to 100% by mass, more preferably 4 to 90% by mass, further preferably 20 to 90% by mass, even more preferably 30 to 90% by mass, and particularly preferably 40 to 80% by mass. By setting it above the lower limit, there is a tendency for the cone angle to decrease. By setting it below the upper limit, there is a tendency to suppress the amount of gas, i.e., smoke, generated during the firing process.

[0606] In the photosensitive resin composition of the present invention, the content ratio of (A) alkali-soluble resin to 100 parts by mass of the total amount of (C) olefinically unsaturated compound and (C2) olefinically unsaturated compound is not particularly limited, but is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, further preferably 250 parts by mass or more, even more preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. Furthermore, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, further preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, further preferably 250 to 500 parts by mass, even more preferably 300 to 450 parts by mass, and particularly preferably 350 to 400 parts by mass. By setting it to the lower limit or above, there is a tendency to achieve a suitable dissolution and development state without peeling or the like. By setting it to the upper limit or below, there is a tendency to obtain a suitable dissolution time for the developer.

[0607] When using an adhesion enhancer, its content is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and even more preferably 0.4 to 2% by mass, relative to the total solids content of the photosensitive resin composition. By setting it to the lower limit or above, there is a tendency to obtain a sufficient effect in improving adhesion. By setting it to the upper limit or below, there is a tendency to suppress the decrease in sensitivity or the presence of residue after development that could become a defect.

[0608] When using a surfactant, its content is not particularly limited, but relative to the total solids content of the photosensitive resin composition, it is preferably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, even more preferably 0.01 to 0.5% by mass, and particularly preferably 0.03 to 0.3% by mass. By setting it to the lower limit or above, there is a tendency to easily exhibit the smoothness and uniformity of the coated film. By setting it to the upper limit or below, there is a tendency to easily exhibit the smoothness and uniformity of the coated film, and also to suppress the deterioration of other properties.

[0609] The photosensitive resin composition of the present invention is adjusted by using a solvent to ensure that the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be adjusted to preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.

[0610] <Physical Properties of Photosensitive Resin Compositions>

[0611] The optical density (OD) per 1 μm film thickness of the photosensitive resin composition coating of the present invention is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, further preferably 0.7 or more, even more preferably 0.9 or more, and preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, further preferably 0.5 to 3.0, even more preferably 0.5 to 2.0, still more preferably 0.7 to 2.0, and particularly preferably 0.9 to 1.5. By setting it to the lower limit or above, there is a tendency to obtain sufficient light-blocking properties. By setting it to the upper limit or below, there is a tendency to suppress the surface roughness of the electrode and increase the residual film rate.

[0612] The optical density (OD) per 1 μm thickness of the coating can be measured using a coating formed by curing the photosensitive resin composition of the present invention. A coating of about 0.5 to 1.5 μm, formed by heating and curing at 230°C for 20 minutes, can be used for measurement.

[0613] Optical density refers to the transmitted light density expressed by ISO visual density in the ISO 5-3 standard, which describes the spectral sensitivity characteristics of the light-receiving part. Typically, an A-level light source as specified by the CIE (International Commission on Illumination) is used as the light source. An example of an instrument suitable for measuring transmitted light density is the X-Rite 361T(V) from SAKATA INX ENG.CO.,LTD.

[0614] [Colorant Dispersion]

[0615] The components and composition of the colorant dispersion constituting the present invention will be described.

[0616] The colorant dispersion of the present invention contains (D) a colorant, (E) a dispersant, and (A) an alkali-soluble resin. In particular, the (D) colorant contains an organic black pigment (D-1) and also contains (C) an olefinic unsaturated compound. A solvent is preferably included.

[0617] The components of the colorant dispersion in this invention may preferably be those listed as the same items in the photosensitive resin composition of this invention.

[0618] <Proportion of each component in the colorant dispersion>

[0619] In the colorant dispersion of the present invention, the content of colorant (D) relative to the total solids content in the colorant dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more. Furthermore, it is typically 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. By setting it to the lower limit or above, a photosensitive resin composition can be manufactured with an appropriate solids content concentration; furthermore, by setting it to the upper limit or below, there is a tendency for good dispersibility. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, particularly preferably 50 to 65% by mass, and most preferably 55 to 65% by mass.

[0620] When the colorant dispersion of the present invention contains an organic black pigment (D-1), the content of the organic black pigment (D-1) relative to the total solids content in the colorant dispersion is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more. Furthermore, it is generally 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. By setting it to the lower limit or above, a photosensitive resin composition can be manufactured with an appropriate solids content concentration; furthermore, by setting it to the upper limit or below, there is a tendency for good dispersibility. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, particularly preferably 50 to 65% by mass, and most preferably 55 to 65% by mass.

[0621] In the colorant dispersion of the present invention, the content of (E) dispersant relative to the total solids content in the colorant dispersion is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. By setting it to the lower limit or above, there is a tendency for the dispersibility to become better; furthermore, by setting it to the upper limit or below, there is a tendency for the residual dispersant to be reduced, and the developability of the resulting photosensitive resin composition to become better. The above-mentioned upper and lower limits can be combined arbitrarily. For example, preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and particularly preferably 8 to 15% by mass.

[0622] When the colorant dispersion of the present invention contains an acrylic dispersant as (E) dispersant, the proportion of the acrylic dispersant relative to the total solids content in the colorant dispersion is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. By setting it to the lower limit or above, there is a tendency for the dispersibility to become better and the pattern adhesion to become better during the development of the cured product; conversely, by setting it to the upper limit or below, there is a tendency for the developability of the resulting photosensitive resin composition to become better. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and particularly preferably 10 to 15% by mass.

[0623] In the colorant dispersion of the present invention, the content of (A) alkali-soluble resin relative to the total solids content in the colorant dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. By setting it to the lower limit or above, there is a tendency for good dispersibility; furthermore, by setting it to the upper limit or below, there is a tendency for the colorant dosage in the obtained photosensitive resin composition to be optimized and sufficient opacity to be ensured. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, even more preferably 20 to 35% by mass, and particularly preferably 25 to 35% by mass.

[0624] It should be noted that the colorant dispersion in this invention uses the above-mentioned organic solvent, and its solid component concentration is preferably adjusted to be 5 to 50% by mass, more preferably 10 to 30% by mass.

[0625] <Physical Properties of Colorant Dispersions>

[0626] The viscosity of the colorant dispersion is preferably 1 MPa·s or higher, more preferably 3 MPa·s or higher, and even more preferably 5 MPa·s or higher. Furthermore, it is preferably 15 MPa·s or lower, and even more preferably 10 MPa·s or lower. The viscosity can be measured, for example, using a rotational viscometer.

[0627] [Method for manufacturing colorant dispersion]

[0628] The colorant dispersion in this invention is manufactured using conventional methods.

[0629] It is preferable to pre-disperse the (D) colorant using a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc. Through dispersion treatment, the (D) colorant is micronized, thus tending to improve the coating properties of the photosensitive resin composition and reduce the surface roughness.

[0630] The dispersion treatment is preferably carried out in a system comprising (D) colorant, (E) dispersant and solvent, and (A) alkali-soluble resin, or all of them. In particular, when a polymeric dispersant is used as (E) dispersant, the thickening of the resulting colorant dispersion and photosensitive resin composition over time is suppressed, i.e., excellent dispersion stability, and is therefore preferred.

[0631] As the colorant (D), dispersant (E), and solvent that can be used in the colorant dispersion, it is preferable to use substances described as substances that can be used in the photosensitive resin composition, respectively.

[0632] When a liquid containing all the components incorporated into a photosensitive resin composition is dispersed, the highly reactive components may be modified due to the exothermic reaction generated during the dispersion process. Therefore, it is preferable to perform the dispersion process in a system containing a polymeric dispersant.

[0633] When using a sand mill to disperse the (D) colorant, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. The dispersion treatment conditions are preferably a temperature of 0°C to 100°C, more preferably room temperature to 80°C. Regarding the dispersion time, the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus, and therefore should be adjusted accordingly. A general standard for dispersion is to control the gloss of the colorant dispersion so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300. If the gloss of the photosensitive resin composition is low, the dispersion treatment is often insufficient, leaving behind coarse colorant particles, which may lead to insufficient developability, adhesion, resolution, and surface roughness. When dispersion treatment continues until the gloss value exceeds the above range, the colorant breaks down, producing a large number of ultrafine particles, thus tending to compromise dispersion stability.

[0634] The preferred particle size of the colorant dispersed in the colorant dispersion is 0.03–0.3 μm, which can be determined by dynamic light scattering.

[0635] [Method for manufacturing photosensitive resin composition]

[0636] The photosensitive resin composition of the present invention is prepared by mixing the various components to form a uniform solution or dispersion.

[0637] In the case where the photosensitive resin composition of the present invention contains colorant (D), the colorant dispersion obtained by the above dispersion treatment is mixed with other components contained in the photosensitive resin composition to prepare a homogeneous solution or dispersion. During the manufacturing process of the photosensitive resin composition, fine debris may sometimes be mixed into the liquid; therefore, it is ideal to filter the obtained photosensitive resin composition using a filter or the like.

[0638] [cured material]

[0639] By curing the photosensitive resin composition of the present invention, the cured product of the present invention can be obtained.

[0640] The cured product obtained by curing the photosensitive resin composition of the present invention can preferably be used as a black matrix, an insulating film, or a spacer, and can be more preferably used as a spacer.

[0641] The thickness of the cured film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 0.9 μm or more. Furthermore, it is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. For example, it is preferably 0.5 to 15 μm, more preferably 0.7 to 10 μm, and even more preferably 0.9 to 5 μm.

[0642] From the viewpoint of light-shielding properties, the optical density (OD) per 1 μm of the cured product of the present invention is preferably 0.2 or more, more preferably 0.5 or more, further preferably 0.7 or more, and particularly preferably 0.9 or more. Furthermore, it is preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. For example, it is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, further preferably 0.5 to 3.0, even more preferably 0.5 to 2.0, still more preferably 0.7 to 2.0, and particularly preferably 0.9 to 1.5. Here, the optical density (OD) is a value measured using the method described later.

[0643] Next, the cured product using the photosensitive resin composition of the present invention will be described according to its manufacturing method.

[0644] (1) Support body

[0645] As a support for forming cured products, the material is not particularly limited as long as it has adequate strength. Substrates are primarily used, but examples of materials 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, thermosetting resin sheets such as poly(meth)acrylic acid resins, and various types of glass. From a heat resistance perspective, glass and heat-resistant resins are preferred. Furthermore, sometimes transparent electrodes such as ITO and IZO, or metal electrodes such as silver, gold, platinum, aluminum, and magnesium, are formed on the surface of the substrate. Besides the aforementioned substrates, it can also be formed on TFT (Thin-Film Transistor) arrays.

[0646] To improve surface properties such as adhesion, the support can be subjected to various resin film formation treatments, such as corona discharge treatment, ozone treatment, silane coupling agents, and urethane resins, as needed.

[0647] The thickness of the support is preferably 0.05 to 10 mm, more preferably in the range of 0.1 to 7 mm. Furthermore, when performing film formation treatment with various resins, the film thickness is preferably 0.01 to 10 μm, more preferably in the range of 0.05 to 5 μm.

[0648] A photosensitive resin composition is supplied in a film or pattern onto a support onto which a cured material is to be formed by means of coating or other methods, and the solvent is dried. Next, a pattern is formed by methods such as photolithography with exposure and development. Afterward, additional exposure and thermal curing are performed as needed, thereby forming a cured material on the substrate.

[0649] (2) Supply method to the support

[0650] The photosensitive resin composition of the present invention is preferably supplied to the support in a dissolved or dispersed state in a solvent. As a supply method, it can be carried out by conventionally known methods, such as spin coating, wire rod coating, flow coating, die coating, roller coating, and spray coating. Furthermore, it can also be supplied in a patterned manner, for example, by inkjet printing or printing. Die coating is preferred from the comprehensive viewpoint of significantly reducing the amount of coating liquid used, completely eliminating the effects of fogging and other contaminant formation as in spin coating, and suppressing foreign matter generation.

[0651] The coating amount varies depending on the application, and is preferably 0.5–10 μm, more preferably 1–9 μm, and particularly preferably 1–7 μm, in terms of dried film thickness. Importantly, the dried film thickness or the height of the final cured product is uniform throughout the entire area of ​​the support. By reducing deviations, the light-shielding properties within the support are uniform. Furthermore, when used as a spacer, a uniform light-emitting layer can be formed, suppressing display defects during luminescence.

[0652] When using the photosensitive resin composition of the present invention to form cured products of different heights simultaneously by photolithography, the final cured products will have different heights.

[0653] (3) Drying method

[0654] Drying after supplying the photosensitive resin composition to the support is preferably carried out using drying methods such as heating plates, IR ovens, or convection ovens. Alternatively, a vacuum drying method can be used, where drying is performed in a vacuum chamber without increasing the temperature.

[0655] The drying conditions can be appropriately selected based on the type of solvent and the performance of the dryer used. The drying time is preferably selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 130°C, and more preferably within the range of 30 seconds to 3 minutes at a temperature of 50 to 110°C, depending on the type of solvent and the performance of the dryer used.

[0656] (4) Exposure method

[0657] Exposure is performed by overlaying a negative mask pattern onto a coated film of the photosensitive resin composition, and then irradiating it with an ultraviolet or visible light source through the mask pattern. When using an exposure mask, methods can be employed such as bringing the exposure mask close to the coated film of the photosensitive resin composition, or placing the exposure mask away from the coated film and projecting exposure light through the mask. Alternatively, scanning exposure using a laser can be employed without a mask pattern. If necessary, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, exposure can be performed in a deoxygenating atmosphere, or after forming an oxygen-blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

[0658] In the case of simultaneously forming cured materials with different heights using photolithography, an exposure mask is used, for example, having a light-shielding portion (0% transmittance) and an opening (intermediate transmission opening) with a lower average transmittance than the opening with the highest average transmittance (fully transmitted opening). According to this method, the difference in residual film yield is generated by the difference in average transmittance between the intermediate transmission opening and the fully transmitted opening, i.e., the difference in exposure amount.

[0659] Methods for creating intermediate transmission openings are known, for example, using a matrix-like light-blocking pattern with tiny polygonal light-blocking units. Methods for controlling light transmittance by using films made of materials such as chromium-based, molybdenum-based, tungsten-based, or silicon-based materials as absorbers are also known.

[0660] There are no particular limitations on the light source used for exposure. Examples of light sources include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. Optical filters can also be used when irradiating light of a specific wavelength.

[0661] As an optical filter, it can be a type that allows the transmittance at the exposure wavelength to be controlled by a thin film. Examples of materials used in this case include Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.

[0662] There is no specific limit to the exposure level, but 1 mJ / cm is preferred. 2 The above is preferred, with 5 mJ / cm being more ideal. 2 The above is further optimized to 10 mJ / cm 2 In addition to the above, the preferred value is 300 mJ / cm. 2 The following is more preferably 200 mJ / cm 2 The following is a further preferred value: 150 mJ / cm 2 the following.

[0663] (5) Development method

[0664] After the above exposure, an image pattern can be formed on the support by developing with an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, surfactants, organic solvents, buffers, complexing agents, dyes, or pigments.

[0665] Examples of basic compounds include: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, and other inorganic basic compounds; monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, and other organic basic compounds. These basic compounds can be used alone or in combination with two or more.

[0666] Examples of surfactants include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0667] Examples of organic solvents include isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents can also be used in combination. Furthermore, an organic solvent can be used alone or in combination with water or an aqueous solution of an alkaline compound.

[0668] There are no particular restrictions on the development conditions, but the development temperature is preferably 10–50°C, more preferably 15–45°C, and even more preferably 20–40°C. Development methods can include, for example, immersion development, spray development, brush development, and ultrasonic development.

[0669] (6) Additional exposure and thermosetting treatment

[0670] The developed substrate may be subjected to additional exposure using the same method as described above, as needed. Alternatively, a heat curing process (also known as a firing process) may be performed after development or additional exposure. For the heat curing process, the preferred temperature is 100–280°C, more preferably 150–250°C, and the time is 5–60 minutes.

[0671] [Block]

[0672] The photosensitive resin composition of the present invention is preferably used to form spacers, particularly spacers for dividing organic layers of organic electroluminescent elements. Examples of organic layers used in organic electroluminescent elements include the hole injection layer, hole transport layer, or hole transport layer on the hole injection layer described in Japanese Patent Application Publication No. 2016-165396.

[0673] When the present invention is used as a spacer, its size, shape, etc. are appropriately adjusted according to the specifications of the organic electroluminescent element to which it is applied, but the optical density (OD) per 1 μm film thickness of the spacer formed by the photosensitive resin composition of the present invention is the same as that of the cured film.

[0674] [Organic electroluminescent element]

[0675] The organic electroluminescent element of the present invention comprises a cured material, such as a spacer wall, formed from the photosensitive resin composition of the present invention.

[0676] For example, various organic light-emitting elements can be manufactured using a substrate having a spacer pattern created by the method described above. The method for forming the organic light-emitting element is not particularly limited, but it is preferable to form an organic layer such as a pixel using a wet process such as vapor deposition, casting, spin coating, or inkjet printing after forming a spacer pattern on the substrate. In the vapor deposition process, the functional material is sublimated under vacuum and deposited onto the area enclosed by the spacers on the substrate to form a film.

[0677] As types of organic electroluminescent elements, bottom-emitting type and top-emitting type can be listed.

[0678] In a bottom-emitting type, for example, spacers are formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are stacked in the openings formed by the spacers. On the other hand, in a top-emitting type, for example, spacers are formed on a glass substrate on which a metal electrode layer is stacked as a reflective layer, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the openings formed by the spacers.

[0679] Organic electroluminescent layers, as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681, can be used. Alternatively, quantum dots, as described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101, can also be used.

[0680] The layer structure is not limited to this. For example, from the viewpoint of luminous efficiency, each layer of the hole transport layer and electron transport layer can be a stacked structure consisting of two or more layers. The thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is preferably 1 to 500 nm.

[0681] Organic light-emitting diodes (OLEDs) can be configured to display RGB colors separately in each opening, or multiple colors can be layered within a single opening. For improved reliability, OLEDs can incorporate a sealing layer. This sealing layer prevents moisture from the air from adsorbing onto the OLED and reducing its luminous efficiency. To improve light extraction efficiency, OLEDs can have a low-reflection film at the air interface. By placing this low-reflection film at the air-electrode interface, the refractive index difference can be reduced, suppressing reflection at the interface. For example, moth-eye structures and multilayer film techniques can be used for such low-reflection films.

[0682] When organic electroluminescent elements are used as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of one pixel from leaking into other pixels. Furthermore, when the electrodes or the like are metal, it is necessary to prevent the degradation of image quality associated with the reflection of external light. Therefore, it is preferable to give the spacers constituting the organic electroluminescent elements light-shielding properties.

[0683] In organic electroluminescent devices, electrodes need to be provided on the upper and lower surfaces of the spacer walls. Therefore, from the viewpoint of insulation, it is preferable that the spacer walls have high resistance and low dielectric constant. Thus, when a colorant is used to impart light-shielding properties to the spacer walls, it is preferable to use the aforementioned organic pigment with high resistance and low dielectric constant.

[0684] [Color filter containing luminescent nanocrystals]

[0685] The color filter containing luminescent nanocrystals of the present invention is not particularly limited as long as it has the spacer wall of the present invention. Examples include color filters in which pixels are formed in the area divided by the spacer wall.

[0686] Figure 1 This is a schematic cross-sectional view of an example of a color filter equipped with the spacer wall of the present invention. (See attached image.) Figure 1 As shown, the color filter 100 includes a substrate 10, spacers 20 disposed on the substrate, red pixels 30, green pixels 40, and blue pixels 50. The red pixels 30, green pixels 40, and blue pixels 50 are arranged in a grid pattern in a repeating order. The spacers 20 are disposed between these adjacent pixels. In other words, these adjacent pixels are separated from each other by the spacers 20.

[0687] Red pixel 30 contains red luminescent nanocrystals 2, and green pixel 40 contains green luminescent nanocrystals 1. Blue pixel 50 is a pixel that transmits blue light from a light source.

[0688] These nanocrystals are nanoscale crystals that absorb excitation light and emit fluorescence or phosphorescence, for example, crystals with a maximum particle size of less than 100 nm as determined by transmission electron microscopy or scanning electron microscopy.

[0689] Luminescent nanocrystals can absorb light of a specified wavelength and then emit light of a different wavelength (fluorescence or phosphorescence). For example, red luminescent nanocrystal 2 emits light with a peak wavelength in the range of 605 to 665 nm (red light), and green luminescent nanocrystal 1 emits light with a peak wavelength in the range of 500 to 560 nm (green light).

[0690] According to the solution of the Schrödinger wave equation in the square well potential model, the wavelength (emission color) of the light emitted by luminescent nanocrystals depends not only on the size (e.g., particle size) of the nanocrystals but also on the band gap they possess. Therefore, by changing the constituent materials and size of the luminescent nanocrystals used, the emission color can be selected. Examples of luminescent nanocrystals include quantum dots.

[0691] The method for manufacturing a color filter containing luminescent nanocrystals is not particularly limited, but examples include: preparing a substrate having spacers formed from the cured product of the present invention, and forming a layer containing luminescent nanocrystals in the region defined by the spacers. The method for forming the layer containing luminescent nanocrystals is not particularly limited; for example, it can be manufactured by selectively attaching an ink composition containing luminescent nanocrystals by inkjet printing, and then curing the ink composition by irradiation with active energy rays or heating.

[0692] [Image display device]

[0693] The image display device of the present invention includes the spacer wall of the present invention. For example, an organic EL display device having an organic electroluminescent element having the spacer wall of the present invention can be cited as an example of the image display device of the present invention.

[0694] As long as an organic EL display device includes the aforementioned organic electroluminescent elements, there are no particular restrictions on the model or structure of the image display device. For example, active-drive organic electroluminescent elements can be used and assembled using conventional methods. For instance, it can be formed using the methods described in "Organic EL Display" (OHM Corporation, published August 20, 2004, authored by Shizushi Tokito, Chinatsu Adachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter for image display, or organic electroluminescent elements emitting different colors, such as RGB, can be combined for image display.

[0695] Example

[0696] The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from its spirit.

[0697] The composition of the photosensitive resin compositions used in the following examples and comparative examples and their evaluation methods are described below.

[0698] <Alkali-soluble resin-I>

[0699] 300 parts by weight of Nippon Kayaku Co., Ltd.'s "XD1000" (a polyglycidyl ether of dicyclopentadiene / phenol polymer, epoxy equivalent 252), 87 parts by weight of acrylic acid, 0.2 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 255 parts by weight of propylene glycol monomethyl ether acetate were added to a reaction vessel and stirred at 100°C until the acid value reached 3.0 mg KOH / g. Next, 145 parts by weight of tetrahydrophthalic anhydride were added, and the reaction was carried out at 120°C for 4 hours to obtain an alkali-soluble resin (I) with a solid content of 50% by weight, an acid value of 106 mg KOH / g, and a weight-average molecular weight (Mw) of 2600 (converted from polystyrene) as determined by GPC.

[0700] <Alkali-soluble resin-II>

[0701] KBR-201, manufactured by KISCO, is a resin with a fluorene-bisphenol backbone. It has a weight-average molecular weight of 5107 and an acid value of 113 mg KOH / g.

[0702] <Photopolymerization Initiator-I>

[0703] Use compounds with the following chemical structures.

[0704] [Chemical Formula 46]

[0705]

[0706] <Alkene Unsaturated Compounds-I>

[0707] [Chemical Formula 47]

[0708]

[0709] 50.0 parts by mass of an epoxy compound with the chemical structure represented by the above formula, 170.3 parts by mass of propylene glycol monomethyl ether acetate, 0.89 parts by mass of 2,4,6-tris(dimethylaminomethyl)phenol, and 0.050 parts by mass of p-methoxyphenol were subjected to nitrogen displacement while stirring and heated to 100°C. 44.3 parts by mass of methacrylic acid were added dropwise over 30 minutes. The reaction was further carried out at 100°C for 8 hours until the acid value was below 10 mg KOH / g, yielding an olefinically unsaturated compound-I with the following chemical structure.

[0710] [Chemical Formula 48]

[0711]

[0712] <Alkene Unsaturated Compounds-II>

[0713] A-9300: Tri-(2-Acryloyloxyethyl)isocyanurate manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0714] <Alkene Unsaturated Compounds-III>

[0715] TAIC: Triallyl isocyanurate manufactured by Shin-Ling Corporation.

[0716] <Alkene Unsaturated Compounds-IV>

[0717] DA-314: DENACOL acrylate manufactured by Nagase ChemteX.

[0718] <Alkene Unsaturated Compounds-V>

[0719] TEPIC-S: Triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.

[0720] <Alkene Unsaturated Compounds-VI>

[0721] MA-DGIC: Monoallyl diglycidyl isocyanurate manufactured by Shikoku Chemical Industry Co., Ltd.

[0722] <Alkene Unsaturated Compounds-VII>

[0723] DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

[0724] <Alkene Unsaturated Compounds-VIII>

[0725] Alkali-soluble resin-II as described in International Publication No. 2022 / 215712.

[0726] <Coloring Agent-I>

[0727] Made by BASF, Irgaphor (registered trademark) Black S 0100CF (has a chemical structure represented by the following formula (D-1-2)).

[0728] [Chemical Formula 49]

[0729]

[0730] <Dispersant-I>

[0731] BYK Corporation manufactures DISPERBYK (registered trademark) LPN-21116.

[0732] <Solvent-I>

[0733] PGMEA: Propylene glycol monomethyl ether acetate.

[0734] Solvent-II

[0735] MB: 3-Methoxy-1-Butanol.

[0736] <surfactants>

[0737] MEGAFACE F-559 manufactured by DIC Corporation.

[0738] <Determination of optical density per unit film thickness (unit OD value)>

[0739] The optical density per unit film thickness was measured according to the following procedure.

[0740] Using a spin coater, the photosensitive resin compositions of each example / comparative example were coated onto a glass substrate to a thickness of 1.5 μm after heat curing (firing). Then, a vacuum dryer was used for 60 seconds. Next, the substrate was heated to 100°C and dried for 100 seconds.

[0741] The resulting coating was exposed without an exposure mask. A Canon MPA-600FA mirror projection exposure machine was used as the illumination source, with an exposure dose of 80 mJ / cm². 2 A 20-second exposure was performed. The illuminance was 500 mW / cm². 2 Next, the substrate is heated and cured in an oven at 230°C for 30 minutes to obtain the resist-coated substrate 1.

[0742] The optical density (OD value) of the resist-coated substrate 1 was measured using an X-Rite 361T(V) transmission density meter (light source color temperature: approximately 2850K (equivalent to CIE standard light source A), light-receiving part spectrophotometry characteristics: ISO visual density under ISO 5-3 standard). The film thickness was measured using a VertScan(R) 2.0 non-contact surface / layer cross-sectional shape measurement system manufactured by Mitsubishi Systems. The optical density (OD value) per unit film thickness (1μm) was calculated based on the optical density (OD value) and film thickness. It should be noted that the OD value represents the light-blocking ability; a higher value indicates higher light-blocking performance.

[0743] Fabrication of a smoke measurement substrate

[0744] First, the weight W1 (mg) of a 5cm × 5cm glass substrate was measured. Using a spin coater, the photosensitive resin compositions of each example / comparative example were coated onto the glass substrate to a thickness of 1.5 μm after heat curing (firing). Then, a vacuum dryer was used for 60 seconds. Next, the substrate was heated to 100°C and dried for 100 seconds to obtain the coated substrate. Then, the obtained coating was exposed without an exposure mask. An intensity of 40 mW / cm² at a wavelength of 365 nm was used as the illumination source. 2The high-pressure mercury lamp was set to an exposure dose of 40 mJ / cm. 2 The weight of the substrate at this point, W2 (mg), was measured. The substrate was then fired in an oven at 230°C for 30 minutes to obtain the smoke emission measurement substrate. The weight of the substrate at this point, W3 (mg), was measured.

[0745] <Evaluation of Smoke Volume>

[0746] The weight W1 of the substrate before coating, the weight W2 of the substrate after exposure, and the weight W3 of the substrate after firing were measured using an analytical balance (Shimadzu Corporation AUW-120D). The amount of smoke during the firing process was calculated using the following formula.

[0747] Smoke content (%) = (Substrate weight after exposure W2 - Substrate weight after firing W3) ÷ (Substrate weight after exposure W1 - Substrate weight before coating W2)

[0748] In addition, the amount of smoke is determined as follows. A indicates the best.

[0749] A: Smoke volume is less than 13%.

[0750] B: Smoke volume is 13% or higher but less than 17%.

[0751] C: Smoke volume is above 17%.

[0752] It should be noted that the amount of smoke indicates the ratio of the amount of gas during the firing process to the amount of coating; the less smoke, the better.

[0753] Fabrication of substrates for evaluating residual film rate

[0754] Using a spin coater, the photosensitive resin compositions of each example / comparative example were coated onto a glass substrate with an indium tin oxide (ITO) film formed on its surface (0.7 mm thick) to achieve a thickness of 1.5 μm after heat curing (firing). Then, a vacuum dryer was used for 60 seconds. Next, the substrate was heated to 100°C and dried for 100 seconds to obtain the coated substrate.

[0755] The film thickness T1 (μm) after heating and drying was determined using the method described later.

[0756] The coated substrate was exposed using a photomask. A Canon mirror projection exposure machine (MPA-600FA) was used with an exposure dose of 80 mJ / cm². 2 A 20-second exposure was performed. The illuminance was 500 mW / cm². 2The slit width is 1.6 mm. The photomask uses a mask with a grid-like opening (with a 50 μm square covering portion, and multiple such covering portions spaced 50 μm apart from the exposure portion).

[0757] Next, using a developer solution containing an aqueous solution of 0.05% by mass potassium hydroxide and 0.08% by mass nonionic surfactant (Kao Corporation's "A-60"), spray development was performed at 24°C and a water pressure of 0.05 MPa. Development was then stopped by rinsing off the developer solution with pure water, followed by a 10-second water rinse spray. The spray development time was set to 1.6 times the time required for the unexposed portions of the coating to dissolve and be removed. Regarding the portion corresponding to the square light-shielding area, since the photosensitive resin composition was washed away after development, the ITO substrate was exposed, forming a hole.

[0758] The substrate was heated and cured in an oven at 230°C for 30 minutes (firing treatment) to obtain a patterned substrate for patternability measurement. The film thickness T2 (μm) was measured at this time.

[0759] <Calculation of Residual Film Ratio>

[0760] The film thickness of the coating at each stage of the patterned substrate (after drying and after firing) was measured using a VertScan® 2.0 non-contact surface / layer cross-sectional shape measurement system manufactured by Mitsubishi Systems. The ratio of the film thickness after firing (T2) to the film thickness after drying (T1) in the film thickness measurement was calculated as the residual film rate.

[0761] Residual film rate (%) = T2 / T1 * 100 (%)

[0762] The calculated residual film rate is judged as follows: A indicates the highest and best residual film rate. If the residual film rate is above 60%, it tends to be practically feasible.

[0763] A: The residual film rate is over 70%.

[0764] B: The residual film rate is 60% or higher but less than 70%.

[0765] C: Residual film rate is less than 60%.

[0766] It should be noted that the residual film rate is related to the exposure sensitivity of the resist, its solubility in the developer, and its thermal decomposition during the firing process. A higher residual film rate is preferred.

[0767] <Determination of Cone Angle>

[0768] To evaluate the cross-sectional shape of the spacer wall of the substrate, a scanning electron microscope (SEM) was used to observe it at 10,000x magnification, and the angle between the substrate and the spacer wall was measured as the cone angle. The smaller the cone angle, the better.

[0769] A: The cone angle is less than 30 degrees.

[0770] B: The cone angle is greater than 30 degrees and less than 50 degrees.

[0771] C: Cone angle greater than 50 degrees.

[0772] <Preparation of Colorant Dispersion-1>

[0773] The colorant, dispersant, alkali-soluble resin, and solvent listed in Table 1 were mixed in the mass ratios listed in Table 1. The mixture was dispersed for 3 hours using a paint shaker within a temperature range of 25–45°C. As beads, [the mixture was used...] Zirconia beads were added to a dispersion at a ratio of 2.5 times their mass. After dispersion, the beads were separated from the dispersion by a filter. Colorant dispersion-1 was prepared.

[0774] It should be noted that the amount of solvent in Table 1 also includes the amount of solvent derived from dispersants and alkali-soluble resins.

[0775] [Table 1]

[0776]

[0777] [Examples 1-6, Comparative Examples 1-6]

[0778] In Examples 1 to 6 and Comparative Examples 1 to 6, each component was added in such a way that the proportion of each component's solid content in the total solid content was as recorded in Tables 2 to 3. A solvent was further added in such a way that PGMEA / MB = 80 / 20 and the proportion of the total solid content was 17% by mass. The mixture was stirred and dissolved to prepare the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6.

[0779] The evaluation results of optical density, residual film rate, cone angle, and smoke amount per unit film thickness are shown in Tables 2 and 3.

[0780] [Table 2]

[0781]

[0782] [Table 3]

[0783]

[0784]

[0785] As shown in Example 1, the photosensitive resin composition using the olefin unsaturated compound (C-1) has a small cone angle, high residual film rate, and low smoke content. It is believed that the olefin unsaturated compound (C-1) has low vaporization and thermal decomposition products during firing due to its development resistance derived from the isocyanuric acid ring, its high boiling point derived from the hydroxyl group in the molecule, and its high exposure sensitivity derived from the acrylate group.

[0786] As can be seen from Examples 2 and 3, by using the olefin unsaturated compound (C-1), although the cone angle increases by using it in combination with the olefin unsaturated compound -VII, the residual film yield can be further improved.

[0787] As can be seen from Examples 4 to 6, by using the olefinic unsaturated compound (C-1), regardless of the increase or decrease of the alkali-soluble resin or the increase or decrease of the colorant, a composition with a small cone angle, high residual film rate and low smoke amount can be provided.

[0788] On the other hand, according to Comparative Example 1, the olefinic unsaturated compound-II has an isocyanuric acid ring and an acrylate group, but no hydroxyl group. Therefore, it vaporizes during the calcination treatment at 230°C, producing a large amount of smoke.

[0789] According to Comparative Example 2, the olefinic unsaturated compound -III has an isocyanuric acid ring but lacks an acrylate group, instead having an allyl group. Therefore, it has low exposure sensitivity and a reduced residual film yield. Furthermore, lacking a hydroxyl group, it vaporizes during calcination at 230°C, resulting in a large amount of smoke.

[0790] According to Comparative Example 3, the olefinic unsaturated compound -IV has hydroxyl and acrylate groups, but no isocyanuric acid ring, and therefore has low development resistance and a large cone angle.

[0791] According to Comparative Examples 4 and 5, olefinic unsaturated compounds -V and -VI have isocyanuric acid rings but do not have acrylate groups, instead having epoxy and allyl groups. Therefore, they have low exposure sensitivity and reduced residual film yield.

[0792] According to Comparative Example 6, the olefinic unsaturated compound-VII has an acrylate group but no isocyanuric acid ring, therefore it has low development resistance, a large cone angle, and no hydroxyl group, thus it produces a lot of smoke.

[0793] According to Comparative Example 7, the olefinic unsaturated compound -VIII has acrylate and isocyanuric acid rings, but few hydroxyl groups. Addition reactions result in anhydrides, making it prone to anhydride decomposition and producing excessive smoke. Furthermore, the increased carboxyl groups lead to lower development resistance and reduced film yield.

[0794] Explanation of reference numerals in the attached figures

[0795] 1: Green luminescent nanocrystals;

[0796] 2: Red luminescent nanocrystals;

[0797] 10: Substrate;

[0798] 20: partition wall;

[0799] 30: Red pixel;

[0800] 40: Green pixels;

[0801] 50: Blue pixels;

[0802] 100: Color Filter.

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an olefinically unsaturated compound. The (C) olefinic unsaturated compound has a structure represented by the following general formula (2). [Chemical Formula 1] In equation (2), R 4 ~R 6 Each independently represents an alkylene group, which is optionally truncated midway by an ether-like oxygen atom, R 7 ~R 9 Each can be used independently to represent a hydrogen atom or a methyl group.

2. The photosensitive resin composition according to claim 1, wherein, The molecular weight of the (C) olefinic unsaturated compound is 500 to 1000.

3. The photosensitive resin composition according to claim 1, wherein, The photosensitive resin composition also contains (D) a colorant and (E) a dispersant.

4. The photosensitive resin composition according to claim 3, wherein, The colorant (D) contains an organic black pigment (D-1).

5. The photosensitive resin composition according to claim 4, wherein, The organic black pigment (D-1) contains benzodifuranone-based organic black pigments.

6. The photosensitive resin composition according to claim 5, wherein, The benzodifuranone-based organic black pigment contains an organic black pigment as a compound represented by the following general formula (D-1-1), its geometric isomer, its salt, or a salt of its geometric isomer. [Chemical Formula 2] In equation (D-1-1), R 611 and R 616 Each can independently represent a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R 612 R 613 R 614 R 615 R 617 R 618 R 619 and R 620 Each independently represents a hydrogen atom, a halogen atom, and R. 621 COOH, COOR 621 COO - CONH2, CONHR 611 CONR 621 R 622 CN, OH, OR 621 COCR 621 、OOCNH2、OOCNHR 621 OOCNR 621 R 622 NO2, NH2, NHR 621 NR 621 R 622 , NHCOR 622 NR 621 COR 622 N=CH2, N=CHR 621 N = CR 621 R 622 SH, SR 621 SOR 621 SO2R 621 SO3R 621 SO3H, SO3 - SO2NH2, SO2NHR 621 or SO2NR 621 R 622 Choose freely R 612 and R 613 R 613 and R 614 R 614 and R 615 R 617 and R 618 R 618 and R 619 and R 619 and R 620 At least one combination of the groups is optionally directly bonded to each other or optionally bonded through an oxygen atom, a sulfur atom, NH or NR atom. 621 Bridges are bonded together; R 621 and R 622 Each can be independently represented as an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, a cycloalkenyl group with 3 to 12 carbon atoms, or an alkynyl group with 2 to 12 carbon atoms.

7. The photosensitive resin composition according to claim 3, wherein, The colorant (D) is present in a proportion of 5% by mass or more relative to the total solids content of the photosensitive resin composition.

8. The photosensitive resin composition according to claim 1, wherein, The content of the (C) olefinic unsaturated compound relative to the total amount of the (C) olefinic unsaturated compound and (C2) unsaturated compounds other than (C) olefinic unsaturated compounds is 4% by mass or more and 90% by mass or less.

9. The photosensitive resin composition according to claim 1, wherein, The proportion of the (A) alkali-soluble resin is 100 parts by mass or more relative to the total amount of the (C) olefinic unsaturated compound and (C2) unsaturated compounds other than (C) olefinic unsaturated compound.

10. The photosensitive resin composition according to claim 1, wherein, The photosensitive resin composition is used to form spacer walls.

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

12. A spacer wall formed from the cured material according to claim 11.

13. An organic electroluminescent element, the organic electroluminescent element comprising the spacer wall according to claim 12.

14. A color filter having a spacer wall as described in claim 12 and comprising luminescent nanocrystals.

15. An image display device comprising a spacer wall according to claim 12.

Images