Photosensitive composition, manufacturing method for resin cured film, partitioning wall, light-emitting element, display device, light conversion pixel, color filter, and image display device

Abstract

A photosensitive composition including: a compound (A) having an ethylenic carbon-carbon double bond; one or two or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors; a photoradical initiator (C); and titanium oxide (D), wherein the proportion of the titanium oxide (D) among all of the nonvolatile components is 5 mass% or greater.

Description

Photosensitive composition, method for producing cured resin film, partition wall, light-emitting element, display device, light-converting pixel, color filter, and image display device

[0001] The present invention relates to a photosensitive composition, a method for producing a cured resin film, a partition wall, a light-emitting element, a display device, a light conversion pixel, a color filter, and an image display device.

[0002] Due to the industrial importance and wide range of application fields of photocurable photosensitive compositions, various improvements have been continuously investigated.

[0003] Patent Document 1 describes an enethiol-based curable composition containing (A) a specific thiol compound and (B) an ene oligomer having an alicyclic or aromatic ring structure and two or more ethylenically unsaturated groups in the molecule, and having a number average molecular weight of 500 to 20,000 in terms of polystyrene.

[0004] Patent Document 2 describes a photocurable resin composition obtained by treating a resin composition containing an ene compound (a), which is an ene compound having two or more functional groups selected from the group consisting of an allyl ether group, a vinyl ether group, an acrylate group, and a methacrylate group in the molecule, or a mixture of two or more of these ene compounds, and a thiol compound (b), which has two or more thiol groups in one molecule, with an oxidizing compound, and further containing a photopolymerization initiator (c).

[0005] Patent Document 3 describes a curable resin composition containing a thiol compound, an ethylenically unsaturated double bond-containing compound having two or more unsaturated double bond groups, and a compound represented by a specific general formula (dihydroxynaphthalene).

[0006] Patent Document 4 describes the use of a stabilizer system that includes at least one radical scavenger component (A), at least one acidic component (B), where the acidic component (B) includes one or more organic acids, and at least one sulfide-based component (C) selected from the group of organic sulfides, in order to stabilize thiol-ene and / or thiol-yne compositions.

[0007] International Publication No. 2014 / 203779 Japanese Patent Application Laid-Open No. 2011-52148 International Publication No. 2011 / 155239 International Publication No. 2022 / 058138

[0008] Generally, it is preferable that the photosensitive composition exhibits minimal change in properties during storage. That is, it is preferable that the photosensitive composition has good storage stability. Photosensitive compositions with good storage stability are industrially preferred because they are less likely to deteriorate during distribution, for example. Various attempts have been made to improve the storage stability of photosensitive compositions. However, at least some of the previous attempts have improved the storage stability of the photosensitive composition, but have sometimes deteriorated other performances. Examples of "other performances" include patterning properties.

[0009] In light of the above circumstances, the present inventors have carried out investigations with the aim of providing a photosensitive composition that has good storage stability and also has good other properties such as patterning properties.

[0010] The present inventors have completed the invention provided below and solved the above problems.

[0011] 1. A photosensitive composition comprising: (A) a compound having an ethylenic carbon-carbon double bond; (B) one or more thiol compounds selected from the group consisting of thiols and thiol precursors; (C) a photoradical initiator; and (D) titanium oxide, wherein the proportion of the titanium oxide (D) in all non-volatile components is 5% by mass or more. 2. The photosensitive composition according to 1., wherein the proportion of the thiol compound (B) in all non-volatile components is 5% by mass or more. 3. The photosensitive composition according to 1. or 2., wherein the proportion of the titanium oxide (D) in all non-volatile components is 30% by mass or less. 4. The photosensitive composition according to any one of 1. to 3., wherein the thiol compound (B) comprises at least one selected from the group consisting of primary thiols and compounds that generate primary thiols by physical stimulation or chemical action. 5. The photosensitive composition according to any one of 1. to 4., wherein the titanium oxide (D) has a median diameter D ５０A photosensitive composition in the form of a powder having a particle size of 50 to 300 nm. 6. The photosensitive composition according to any one of 1. to 5., wherein the titanium oxide (D) comprises rutile-type titanium oxide. 7. The photosensitive composition according to any one of 1. to 6., wherein the content of a polymerization inhibitor in all non-volatile components is 0 to 1 mass %. 8. The photosensitive composition according to any one of 1. to 7., wherein the content of a silane coupling agent in all non-volatile components is 0 to 1 mass %. 9. The photosensitive composition according to any one of 1. to 8., further comprising an alkali-soluble resin (E). 10. The photosensitive composition according to any one of 1. to 9., further comprising a liquid repellent (F). 11. The photosensitive composition according to any one of 1. to 10. 12. The photosensitive composition according to any one of 1. to 11., further comprising a colorant (G). 13. The photosensitive composition according to any one of 1. to 10., further comprising quantum dots (H), and used to form photoconversion pixels. 14. A method for producing a cured resin film, comprising: a film-forming step of applying the photosensitive composition according to any one of 1. to 13. onto a substrate to form a film; an exposure step of pattern-exposing the film; a development step of developing the exposed film; and a heating step of heating and curing the developed film. 15. A method for producing a cured resin film according to 14., wherein in the heating step, the developed film is heated at 50 to 150°C. 16. 14. or 15. 16. A method for producing a cured resin film according to any one of items 14 to 15., wherein in the heating step, the developed film is heated at 50 to 100°C. 17. A method for producing a cured resin film according to any one of items 14 to 16., wherein in the film-forming step, the applied photosensitive composition is heated at 50 to 150°C. 18. A partition wall composed of a cured product of the photosensitive composition according to any one of items 1 to 12. 19. A partition wall according to item 18., wherein the partition wall is for a light-emitting element.20. A light-emitting device comprising the partition wall according to 18. or 19., and a light-emitting layer or a wavelength conversion layer disposed in an area partitioned by the partition wall. 21. A display device comprising the light-emitting element according to 20. 22. A photoconversion pixel formed of a cured product of the photosensitive composition according to 13. 23. A color filter including the photoconversion pixel according to 22. 24. An image display device comprising the color filter according to 23.

[0012] According to the present invention, there is provided a photosensitive composition which has good storage stability and also has good other properties such as patterning properties.

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0015] In the description of groups (atomic groups) herein, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). The term "(meth)acrylic" in this specification represents a concept that encompasses both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate." In this specification, the term "organic group" refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound. In this specification, the term "non-volatile components" refers to all components other than the solvent described below, unless otherwise specified.

[0016] <Photosensitive Composition> The photosensitive composition of this embodiment comprises: a compound (A) having an ethylenic carbon-carbon double bond; one or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors; a photoradical initiator (C); and titanium oxide (D). In the photosensitive composition of this embodiment, the proportion of titanium oxide (D) in all nonvolatile components is 5 mass% or more.

[0017] Hereinafter, the compound (A) having an ethylenic carbon-carbon double bond may be simply referred to as "compound (A)." Furthermore, one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors may be simply referred to as "thiol-based compounds (B)."

[0018] In an attempt to improve the storage stability of a photosensitive composition, the present inventors discovered that the storage stability of a photosensitive composition containing compound (A), thiol-based compound (B), and photoradical initiator (C) can be improved by incorporating a relatively large amount of titanium oxide (D) into the composition. They also discovered that even when a relatively large amount of titanium oxide (D) is incorporated into the composition, patterning properties are maintained and are unlikely to deteriorate. Although the details are unclear, it is possible that the chemical structure of titanium oxide, particularly on the surface, captures radical species or decomposition products generated from compound (A), thiol-based compound (B), and / or photoradical initiator (C) during storage, or suppresses the generation of radicals or decomposition itself.

[0019] Incidentally, attempts have been made in the past to improve storage stability by adding, for example, a polymerization inhibitor to a photosensitive composition. However, a side effect of the polymerization inhibitor is that patterning ability tends to be reduced. However, in this embodiment, even when titanium oxide (D) is used, patterning ability does not decrease significantly. One presumed reason for this is that titanium oxide (D) is usually particulate and is present non-uniformly in the composition. Conventional polymerization inhibitors are present uniformly in the composition, resulting in reduced patterning ability throughout the entire film formed from the photosensitive composition. However, titanium oxide (D) is present non-uniformly in the composition, and therefore it is believed that there are areas in the film formed from the photosensitive composition where little or no titanium oxide (D) is present. It is possible that the chemical reaction proceeds sufficiently in these areas, thereby suppressing the decrease in patterning ability. Furthermore, titanium oxide (D) is believed to have lower radical scavenging ability than polymerization inhibitors. This "low scavenging ability" leads to reduced scavenging of the large amount of radicals generated during exposure, thereby suppressing the decrease in patterning ability. On the other hand, even if the scavenging ability is low, it is thought that it is still possible to capture trace amounts of radicals generated by degradation over time. This may also be one reason why the storage stability is improved while suppressing deterioration in patterning ability.

[0020] The photosensitive composition of this embodiment will now be described.

[0021] (Compound (A)) The photosensitive composition of this embodiment contains a compound (A) having an ethylenic carbon-carbon double bond. As the compound (A), any compound having an ethylenic carbon-carbon double bond can be used without any particular limitation. The term "ethylenic carbon-carbon double bond" refers to a carbon-carbon double bond that can react by the action of a radical. A conjugated and stabilized double bond such as a double bond in a benzene ring does not fall under the category of "ethylenic carbon-carbon double bond." From the viewpoint of improving reactivity, it is preferable that the compound (A) has an ethylenic carbon-carbon double bond at its terminal.

[0022] The compound (A) may be monofunctional or polyfunctional. That is, the compound (A) may have only one ethylenic carbon-carbon double bond per molecule, or may have two or more (specifically, 2 to 8, more specifically, 2 to 6) ethylenic carbon-carbon double bonds per molecule. From the viewpoints of further improving sensitivity and improving the physical properties of a cured film, it is preferable that the compound (A) is polyfunctional.

[0023] The compound (A) is preferably a (meth)acrylate compound, that is, a compound having a (meth)acryloyl group as a structure containing an ethylenic carbon-carbon double bond, and more preferably a (meth)acrylate compound.

[0024] Specific examples of the compound (A) include the following: Of course, the compound (A) is not limited to these.

[0025] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; urethane (meth)acrylates obtained by reacting polyisocyanate with a hydroxy group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, etc.

[0026] The photosensitive composition of this embodiment may contain only one compound (A), or may contain two or more compounds (A). The content of compound (A) is usually 5 to 60 mass%, preferably 10 to 55 mass%, and more preferably 15 to 50 mass%, of the total nonvolatile components of the photosensitive composition. The content of double bonds (C═C) in compound (A) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and more preferably 10 to 30 mass%.

[0027] (Thiol Compound (B)) The photosensitive composition of this embodiment contains one or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors.

[0028] The thiol compound (B) may be monofunctional or polyfunctional. That is, the thiol compound (B) may have only one mercapto group (or latent mercapto group) per molecule, or may have two or more (specifically, 2 to 8) mercapto groups (or latent mercapto groups) per molecule. From the viewpoint of improving the physical properties of a cured film, the thiol compound (B) is preferably polyfunctional.

[0029] As the thiol in the thiol compound (B), a compound represented by the following general formula (b) can be preferably mentioned.

[0030]

[0031] In the general formula (b), R is a hydrogen atom, an alkyl group, or a cycloalkyl group, and X is —CO— or —CH ２ -, L is an n-valent linking group, and n is an integer of 2 or more, preferably 2 to 8, more preferably 2 to 6. Multiple Rs may be the same or different from each other. Furthermore, multiple Xs may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that multiple Rs are the same as each other, and it is preferable that multiple Xs are the same as each other.

[0032] The alkyl group for R may be linear or branched. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. Of these, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0033] Examples of L, which is an n-valent linking group, include a linear or branched alkylene chain (having, for example, 2 to 6 carbon atoms), a trimethylolpropane residue, -(CH ２ ) ｐ Examples include trivalent linking groups such as an isocyanuric ring having three - (p is 2 to 6), tetravalent or pentavalent linking groups such as a pentaerythritol residue, and hexavalent linking groups such as a dipentaerythritol residue.

[0034] Commercially available thiols in the thiol compound (B) include, for example, the "Karends" series manufactured by Showa Denko K.K. The thiols in this series are secondary thiols. Other examples include products sold by SC Organic Chemical Co., Ltd. under product numbers PEMP, TMMP, DPMP, and TEMPIC. These thiols are primary thiols.

[0035] The "thiol precursor" in the thiol compound (B) refers to a compound that does not itself have a mercapto group, but generates a mercapto group in the composition upon physical stimulation or chemical action. The thiol precursor can be, for example, a thioester, a dithioester, a thiocarbamate, a dithiocarbamate, a thiocarbonate, a xanthogenate, or a trithiocarbonate. The specific structure of the thiol precursor can be, for example, one in which the —SH moiety in the above general formula (b) is esterified or in the form of a salt. Thiol precursors are described, for example, in JP-A-2004-517979.

[0036] The thiol compound (B) preferably contains at least one selected from the group consisting of primary thiols and compounds that generate primary thiols through physical stimulation or chemical action. Based on past knowledge, while primary thiols are highly reactive, they tend to reduce the storage stability of the composition. However, in the photosensitive composition of this embodiment, due to the action of titanium oxide (D), good storage stability can be expected even when a primary thiol is contained. Furthermore, the use of a primary thiol can be expected to provide effects such as even higher sensitivity.

[0037] The content of mercapto groups in the thiol compound (B) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and more preferably 10 to 30 mass%, based on the molecular weight of the thiol compound (B). When the thiol compound (B) is a thiol precursor, this value is calculated based on the chemical structure after the thiol precursor is converted into the thiol compound.

[0038] The photosensitive composition of the present embodiment may contain only one thiol-based compound (B), or may contain two or more thiol-based compounds (B).

[0039] The content of the thiol compound (B) is not particularly limited, but in one embodiment, it is preferably 5% by mass or more, more preferably 5 to 70% by mass, even more preferably 10 to 70% by mass, particularly preferably 15 to 60% by mass, and particularly preferably 20 to 55% by mass of the total non-volatile components of the photosensitive composition. The content of the thiol compound (B) is, for example, 15 to 80 parts by mass, preferably 30 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 70 parts by mass, relative to 100 parts by mass of the compound (A). Incidentally, when the thiol compound (B) is used in this amount, it is believed that the photosensitive composition cures primarily through the thiol-ene reaction, which is known as a bond-forming reaction between a thiol and an alkene.

[0040] In another embodiment, the content of the thiol compound (B) is, for example, 0.1 to 10 mass%, specifically 0.5 to 8 mass%, more specifically 1 to 5 mass%, and even more specifically 1 to 3 mass%, based on the total nonvolatile components of the photosensitive composition. The content of the thiol compound (B) is, for example, 0.2 to 25 mass parts, specifically 1 to 20 mass parts, and more specifically 2 to 15 mass parts, relative to 100 mass parts of the compound (A). When the thiol compound (B) is used in this amount, it is believed that the thiol compound (B) functions primarily as a chain transfer agent and is involved in adjusting the chain length of the polymer produced by the radical polymerization reaction of the compound (A). Depending on the ratio of the compound (A) to the thiol compound (B), both the radical polymerization reaction of the compound (A) and the thiol-ene reaction may occur.

[0041] (Photoradical initiator (C))

[0042] The photosensitive composition of this embodiment contains a photoradical initiator (C). Specific examples of photoradical initiators include intramolecular cleavage initiators in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction initiators in which radicals are generated in combination with a hydrogen donor such as a tertiary amine or ether. Any of these may be used in this embodiment. Of course, photoradical initiators other than these may also be used.

[0043] Specific examples of the photoradical initiator include oxime ester-based, benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based photoradical initiators.

[0044] Specific examples of the oxime ester photoradical initiator include CGI-325 manufactured by BASF, IRGACURE OXE01 (1-[4-(phenylthio)phenyl]-1,2-octadione-2-(o-benzoyloxime), IRGACURE OXE02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(o-acetyloxime)), and N-1919 manufactured by ADEKA Corporation.

[0045] Specific examples of the benzophenone-based photoradical initiator include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0046] Specific examples of the acetophenone-based photoradical initiator include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0047] Specific examples of the diketone-based photoradical initiator include 4,4'-dimethoxybenzyl, methyl benzoylformate, 9,10-phenanthrenequinone, etc. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0048] Specific examples of the acylphosphine oxide initiator include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0049] Specific examples of the quinone initiator include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0050] Specific examples of the acyloin initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Among these, benzoin and benzoin methyl ether are preferred.

[0051] Among commercially available photoradical initiators, preferred ones include those manufactured by BASF under the trade names Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 651, Omnirad 819, Omnirad 907, Omnirad 2959, Omnirad OXE-01, Omnirad OXE-02, Omnirad OXE-03, Omnirad OXE-04, Darocur 1173, and Lucirin TPO; and those manufactured by Tronly under the trade name TR-PBG-305.

[0052] The photosensitive composition of this embodiment may contain only one photoradical initiator (C), or may contain two or more photoradical initiators (C). The content of the photoradical initiator (C) may be adjusted appropriately, taking into consideration sufficient curability and other factors. The content of the photoradical initiator (C) is typically 0.1 to 10 mass%, preferably 0.3 to 8 mass%, and more preferably 0.5 to 5 mass%, of the total nonvolatile components of the photosensitive composition. From another perspective, the amount of the photoradical initiator (C) relative to 100 mass parts of the compound (A) is typically 0.2 to 25 mass parts, preferably 0.5 to 20 mass parts, and more preferably 1 to 15 mass parts.

[0053] (Titanium oxide (D)) The photosensitive composition of the present embodiment contains titanium oxide (D). Titanium oxide (D) is usually in a powder form. In consideration of availability and dispersibility in the composition, the median diameter D of titanium oxide (D) is ５０ is preferably 50 to 300 nm, more preferably 100 to 200 nm. ５０ When titanium dioxide (D) is commercially available, the value provided by the manufacturer (catalog value) can be used. ５０ If the particle size distribution is unknown, D is calculated based on the volumetric particle size distribution calculated using the laser diffraction / scattering method. ５０ can be determined. ５０ By using titanium oxide (D) having a particle size of 300 nm or less, the specific surface area of ​​titanium oxide (D) increases, which makes it easier to come into contact with other components, and therefore it is expected that the storage stability will be further improved. ５０ It is considered that by using titanium oxide (D) having a particle size of 50 nm or more, the effect of suppressing the deterioration of patterning properties due to the above-mentioned "non-uniform presence of titanium oxide (D) in the composition" can be easily obtained.

[0054] The composition of titanium oxide used in this embodiment is usually TiO ２It is represented by the formula: In view of the effect of improving storage stability and ease of availability, it is preferable that the titanium oxide (D) contains rutile-type titanium oxide. As the titanium oxide (D), for example, one that is available on the market as a pigment can be used. Of course, it is also possible to use titanium oxide that is available on the market for purposes other than pigment.

[0055] From the viewpoint of preventing aggregation and sedimentation in the composition, it is preferable that the titanium oxide (D) has been subjected to a dispersion treatment using a dispersant or a binder.

[0056] The photosensitive composition of this embodiment may contain only one titanium oxide (D), or may contain two or more titanium oxides (D). As described above, the proportion of titanium oxide (D) in the total nonvolatile components of the photosensitive composition is 5% by mass or more. The presence of a sufficient amount of titanium oxide (D) in the composition reliably improves storage stability. Furthermore, the proportion of titanium oxide (D) in the total nonvolatile components of the photosensitive composition is preferably 30% by mass or less, from the viewpoint of sufficiently incorporating other components into the composition. In other words, the proportion of titanium oxide (D) in the total nonvolatile components of the photosensitive composition is at least 5% by mass, preferably 5 to 30% by mass, more preferably 15 to 30% by mass, and even more preferably 20 to 30% by mass.

[0057] (Alkali-Soluble Resin (E)) The photosensitive composition of the present embodiment preferably contains an alkali-soluble resin (E). Use of the alkali-soluble resin (E) tends to facilitate the formation of a pattern of a desired shape, particularly when forming a pattern using an alkaline developer. The alkali-soluble resin (E) typically has an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group and a phenolic hydroxy group. Incidentally, in this specification, a resin that has a fluorine atom and is alkali-soluble is generally classified as a liquid repellent (F) described below. In other words, the alkali-soluble resin (E) generally does not have a fluorine atom.

[0058] The alkali-soluble resin (E) may be, for example, an alkali-soluble novolak resin, which can be obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst. Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more. Specific examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

[0059] Examples of the alkali-soluble resin (E) include alkali-soluble epoxy resins and acid-modified epoxy (meth)acrylate resins derived from epoxy resins. The epoxy resins or acid-modified epoxy (meth)acrylate resins may have polymerizable substituents such as hydroxyl groups or (meth)acryloyl groups in their side chains. Examples of epoxy resins include bisphenol-type epoxy resins, and examples of acid-modified epoxy (meth)acrylate resins include those obtained by reacting bisphenol-type epoxy resins with (meth)acrylic acid. Specific examples include bisphenol-type epoxy resins or acid-modified epoxy (meth)acrylate resins having a structural unit represented by the following general formula (e):

[0060]

[0061] In general formula (e), two R's each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and Z represents a monovalent organic group or a hydrogen atom, provided that in at least some of the structural units represented by general formula (e) in the alkali-soluble resin (E), Z is a monovalent organic group having a carboxy group.

[0062] When R is a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 carbon atoms, specific examples of R include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group is preferred from the viewpoint of availability. Specific examples of linear perfluoroalkyl groups having 1 to 3 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Of these, a trifluoromethyl group is preferred from the viewpoint of availability. Each R may have the same structure or different structures.

[0063] When Z is a monovalent organic group, Z is preferably an alkyl group having 1 to 10 carbon atoms. This alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. At least one hydrogen atom in the monovalent organic group of Z may be substituted with a carboxy group or a hydroxy group. This increases alkali solubility.

[0064] The carboxyl group or hydroxyl group of the alkyl group having 1 to 10 carbon atoms represented by Z may be reacted with an esterifying agent. Examples of esterifying agents include acid halides, acid anhydrides, and condensing agents. When Z is a hydrogen atom, -O-Z may be reacted with an esterifying agent. Examples of esterifying agents include the same esterifying agents described above. Examples of acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, and 1,2,3,4-tetrahydrophthalic anhydride. Reacting these acid anhydrides with a resin can introduce ethylenically unsaturated bonds and carboxyl groups into the resin. The amount of carboxyl groups or hydroxyl groups in the alkali-soluble resin to be reacted with the acid anhydride may be appropriately adjusted, taking into account the solubility in alkali required for the alkali-soluble resin.

[0065] Epoxy (meth)acrylate resins having a structural unit represented by general formula (e) are available from, for example, Nippon Kayaku Co., Ltd.

[0066] In addition, alkali-soluble epoxy resins or acid-modified epoxy (meth)acrylate resins other than those mentioned above can also be used. Specific examples include alkali-soluble novolac-type epoxy resins, biphenyl-type epoxy resins, and acid-modified epoxy (meth)acrylate resins derived from these epoxy resins. Commercially available acid-modified epoxy (meth)acrylates can also be used. Examples of commercially available acid-modified epoxy acrylates that can be used include those manufactured by Nippon Kayaku Co., Ltd. under the product names: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H.

[0067] The alkali-soluble resin (E) may have a polycyclic aromatic skeleton such as a fluorene skeleton. The use of such an alkali-soluble resin (E) may improve the heat resistance and durability of the cured pattern. Specific examples of the acid-modified epoxy (meth)acrylate resins described above may include those having a polycyclic aromatic skeleton, or resins having a polycyclic aromatic skeleton may be selected from a different family of resins than the acid-modified epoxy (meth)acrylate resins. Incidentally, resins having a fluorene skeleton are sometimes referred to as "cardo resins." Like other alkali-soluble resins (E), alkali-soluble resins (E) having a polycyclic aromatic skeleton such as a fluorene skeleton preferably have an alkali-soluble group such as a carboxy group or a hydroxy group.

[0068] The alkali-soluble resin (E) may have an ethylenic carbon-carbon double bond. It is believed that the alkali-soluble resin (E) having an ethylenic carbon-carbon double bond forms a bond with the compound (A) during curing of the composition and is incorporated into the cured product. This is believed to contribute to improving the stability and heat resistance of the cured product. Just to be clear, the alkali-soluble resin having an ethylenic carbon-carbon double bond is not classified as the compound (A).

[0069] The weight average molecular weight of the alkali-soluble resin (E) is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive composition. The acid value of the alkali-soluble resin (E) (the number of milligrams of potassium hydroxide required to neutralize 1 g of sample) can be an indicator of alkali solubility. In this embodiment, the acid value of the alkali-soluble resin (E) is preferably 20 to 80, more preferably 30 to 70, and even more preferably 40 to 60. The acid values ​​of the alkali-soluble resins used in the examples described below are on this order.

[0070] When an alkali-soluble resin (E) is used, only one alkali-soluble resin (E) may be used, or two or more alkali-soluble resins (E) may be used. When an alkali-soluble resin (E) is used, the amount thereof is usually 10 to 70 mass %, preferably 15 to 60 mass %, more preferably 20 to 55 mass %, of the total nonvolatile components of the photosensitive composition.

[0071] (Liquid Repellent Agent (F)) When the photosensitive composition of this embodiment is applied particularly to the formation of partition walls, the photosensitive composition of this embodiment preferably contains a liquid repellent agent (F). By forming a pattern (partition wall) having concaves and convexes using a photosensitive composition containing a liquid repellent agent (F), the resulting pattern (partition wall) becomes more likely to repel ink used to form an organic layer. This contributes to preventing ink dropped into a recess from "crawling" up the side surface of the recess and entering an adjacent recess. In other words, it is possible to prevent unintended mixing of dye between pixels.

[0072] The liquid repellent (F) that can be used is not particularly limited, but examples thereof include fluororesins and silicon-containing compounds such as siloxane compounds, which are easily available or produced. The following describes the liquid repellent (F) that can be preferably used, focusing on fluororesins. The liquid repellent (F) is preferably a fluororesin having a structure represented by the following general formula (1), and more preferably a fluororesin having a structure represented by the following general formula (2).

[0073]

[0074] In the general formula (1), two Rf's each independently represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or a fluorine atom; ２ represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0075]

[0076] In the general formula (2), two Rf's each independently represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or a fluorine atom; １ represents a hydrogen atom, a fluorine atom or a methyl group; R ２ represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0077] In general formula (2), R １ is preferably a hydrogen atom or a methyl group. ２ Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group. A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred, and a hydrogen atom and a methyl group are more preferred.

[0078] Rf in general formula (1) or general formula (2) is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, an n-nonafluorobutyl group, an isononafluorobutyl group, or a tert-nonafluorobutyl group, more preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, or a hexafluoroisopropyl group, and particularly preferably a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

[0079] Preferred specific structures of the structural units include the structures described in paragraphs 0060 to 0061 of WO 2021 / 235541.

[0080] The content of the structural unit represented by general formula (2) in the fluororesin serving as the liquid repellent agent (F) is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and particularly preferably 10 to 30 mass %, taking into consideration solubility in solvents, resistance to various treatments in the manufacture of light-emitting elements, and the like.

[0081] The liquid repellent agent (F) may contain a fluororesin containing a structure represented by the following general formula (3).

[0082]

[0083] In general formula (3), R ３ , R ４ each independently represents a hydrogen atom or a methyl group.

[0084] In the general formula (3), W １represents a divalent linking group. Preferably represents -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W １ However, the group —O—C(═O)—NH— is preferable because it provides better liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element.

[0085] In general formula (3), A １ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0086] Divalent Linking Group A １ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0087] Divalent Linking Group A １ When is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0088] Divalent Linking Group A １ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0089] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, and a hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0090] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group exemplified above is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0091] Among them, the divalent linking group A １ is a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group and a 2-hydroxy-n-propylene group are particularly preferred.１ As the ２ -) ２ CH ３ and the like, and the tetravalent linking group A １ As C(CH ２ -) ４ Examples include:

[0092] In the general formula (3), Y １ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0093] In general formula (3), u represents an integer of 1 to 3, and u is particularly preferably 1. In general formula (3), n represents an integer of 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are each independently ortho-, meta-, or para-positions, and preferably para-positions. １ may be the same or different. １ may be the same or different. １ may be the same or different. ４ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of W １ are preferably the same as each other, and a plurality of A １ are preferably the same, and a plurality of Y １ are preferably the same, and a plurality of R ４ are preferably the same as each other.

[0094] Specific preferred examples of the structure represented by general formula (3) include the structures described in paragraphs 0081 to 0084 of WO 2021 / 235541.

[0095] The content of the structural unit represented by general formula (3) in the fluororesin serving as the liquid repellent agent (F) is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and particularly preferably 10 to 30 mass %, taking into consideration solubility in solvents, resistance to various treatments in the manufacture of light-emitting elements, and the like.

[0096] The liquid repellent agent (F) may be a fluororesin containing a structure represented by the following general formula (4).

[0097]

[0098] In general formula (4), R ５ , R ６ each independently represents a hydrogen atom or a methyl group.

[0099] In formula (4), W ２ represents a divalent linking group, preferably -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W ２ is preferably —O—C(═O)—NH—, since the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element is superior.

[0100] In general formula (4), A ２ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ In the general formula (4), A ３ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group can be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0101] Divalent Linking Group A ２ , A ３ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0102] Divalent Linking Group A ２ , A ３ When each of the groups independently represents a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0103] Divalent Linking Group A ２ , A ３ When each of the groups independently represents a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0104] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0105] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0106] Among them, the divalent linking group A ２ , A ３ each independently represents a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ The trivalent linking group A3 is preferably —C(CH ２ -) ２ CH ３ The tetravalent linking group A3 can be C(CH ２ -) ４ Examples include:

[0107] In the general formula (4), Y ２ , Y ３ each independently represents a divalent linking group, and is preferably —O— or —NH—, and more preferably —O—.

[0108] In the general formula (4), n represents an integer of 1 to 3. It is particularly preferable that n is 1. ３ may be the same or different. ６ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of Y ３ are preferably the same, and a plurality of R ６ are preferably the same as each other.

[0109] In the general formula (4), r represents 0 or 1. When r is 0, it is represented by "(-C(=O)-)". ｒ represents a single bond.

[0110] Specific preferred examples of the structure represented by general formula (4) include the structures described in paragraphs 1005 to 0109 of WO 2021 / 235541.

[0111] The content of the structural unit represented by general formula (4) in the fluorine-containing resin serving as the liquid repellent agent (F) is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration the solubility in a solvent and the adhesion of the pattern (partition wall) to the substrate.

[0112] The liquid repellent agent (F) may be a fluororesin containing a structural unit represented by general formula (5).

[0113]

[0114] In general formula (5), R ７ represents a hydrogen atom or a methyl group.

[0115] In general formula (5), R ８ represents a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, in which any number of hydrogen atoms are substituted with fluorine atoms, and the fluorine content in the structural unit is 30 mass% or more.

[0116] R ８When is a linear hydrocarbon group, specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a linear alkyl group having 10 to 14 carbon atoms in which any number of hydrogen atoms have been substituted with fluorine atoms.

[0117] R ８ When is a linear hydrocarbon group, the structural unit represented by general formula (5) is preferably a structural unit represented by the following general formula (5-1):

[0118]

[0119] In general formula (5-1), R ９ is R in general formula (5) ７ is synonymous with.

[0120] In the general formula (5-1), X is a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

[0121] In the general formula (5-1), p is an integer of 1 to 4, and q is an integer of 1 to 14. It is particularly preferable that p is an integer of 1 or 2, and q is an integer of 2 to 8.

[0122] Specific preferred examples of the structural unit represented by general formula (5) include the structures described in paragraphs 0125 to 0128 of WO 2021 / 235541.

[0123] The content of the structural unit represented by general formula (5) in the fluororesin serving as the liquid repellent (F) may be appropriately determined taking into consideration the ease with which the fluororesin repels ink when formed into a pattern (partition wall), the ease with which the fluororesin dissolves in a solvent when the photosensitive composition is prepared, etc. Specifically, the content of the structural unit represented by general formula (5) in the fluororesin serving as the liquid repellent (F) is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and particularly preferably 10 to 30 mass %.

[0124] The fluorine-containing resin that is the liquid repellent agent (F) may contain a structure represented by the following general formula (6).

[0125]

[0126] In general formula (6), R１０ represents a hydrogen atom or a methyl group.

[0127] In the general formula (6), each B independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or —C(═O)—O—R １１ (R １１ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, in which any number of hydrogen atoms are substituted with fluorine atoms; R １１ the fluorine content in the compound is 30% by mass or more) or —O—C(═O)—R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. In addition, m represents an integer of 0 to 3.

[0128] Specific preferred examples of the structure represented by general formula (6) include the structures described in paragraphs 0137 to 0138 of WO 2021 / 235541.

[0129] The content of the structural unit represented by general formula (6) in the fluororesin serving as the liquid repellent (F) is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and particularly preferably 20 to 40 mass%, in consideration of sufficiently obtaining the effect based on the structural unit represented by general formula (6) and solvent solubility.

[0130] In the general formula (6), B １ is a hydroxy group or a carboxyl group, the structural unit represented by general formula (6) has solubility in an alkaline developer. Therefore, when particularly good alkaline developability is desired, the fluorine resin that is the liquid repellent (F) is １ It is preferable that the structural unit contains a structural unit represented by general formula (6) in which is a hydroxy group or a carboxyl group.

[0131] The fluorine-containing resin that is the liquid repellent agent (F) may contain a structure represented by the following general formula (7).

[0132]

[0133] In general formula (7), R １３represents a hydrogen atom or a methyl group.

[0134] In the general formula (7), A ４ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0135] Divalent Linking Group A ４ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0136] Divalent Linking Group A ４ When is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0137] Divalent Linking Group A ４ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0138] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２-), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0139] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0140] Among them, the divalent linking group A ４ is a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２-), 2-hydroxyethylene group (-CH ２ CH(OH)—) is particularly preferred.

[0141] In the general formula (7), Y ４ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0142] In general formula (7), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0143] In the general formula (7), E １ represents a hydroxy group, a carboxyl group, or an oxirane group. １ When is an oxirane group, examples include an ethylene oxide group, a 1,2-propylene oxide group, a 1,3-propylene oxide group, etc. Among these, an ethylene oxide group is preferred.

[0144] In the general formula (7), s represents 0 or 1. When s is 0, (-Y ４ -A ４ When r is 0 and s is 0, the main chain of the structural unit does not contain E １ The resulting structure is a bonded structure.

[0145] Specific preferred examples of the structure represented by general formula (7) include the structure described in paragraph 0156 of WO 2021 / 235541.

[0146] The weight-average molecular weight of the fluororesin serving as the liquid repellent (F), measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000. Adjusting the weight-average molecular weight may increase the strength of the pattern (partition walls) to be formed or may increase the solubility in solvents and improve coatability.

[0147] The dispersity (Mw / Mn) of the fluororesin (F) serving as the liquid repellent (F) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, and particularly preferably from 1.01 to 3.00.

[0148] The fluorine-containing resin serving as the liquid repellent (F) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of dispersing the respective properties appropriately rather than locally, a random copolymer is preferred.

[0149] The fluorine content of the liquid repellent (F) is preferably 20 to 50% by mass, more preferably 25 to 40% by mass. When the fluorine content is within this range, the liquid repellent (F) is easily dissolved in a solvent. Furthermore, when the fluorine content of the liquid repellent (F) is within this range, a pattern (partition wall) with excellent liquid repellency is easily obtained. The fluorine content of the liquid repellent (F), such as a fluororesin, can be measured, for example, in accordance with the description in paragraph 0174 of WO 2021 / 235541.

[0150] When the liquid repellent agent (F) is used, only one liquid repellent agent (F) may be used, or two or more liquid repellent agents (F) may be used. In order to achieve a balance between sufficient liquid repellency of the resulting pattern (partition wall) and good alkaline developability, the amount of the liquid repellent agent (F) used is usually 0.01 to 10 mass %, preferably 0.1 to 8 mass %, and more preferably 0.2 to 5 mass %, of the total nonvolatile components of the photosensitive composition.

[0151] In addition, for fluororesins that can be used as the liquid repellent (F), reference can be made to the description in, for example, WO 2021 / 235541.

[0152] (Colorant (G)) The photosensitive composition of the present embodiment may contain a colorant (G). For example, by using the colorant (G) to color the resulting pattern (partition wall) black, unintended "light leakage" and "color mixing between adjacent pixels" in the light-emitting element can be suppressed. In this specification, titanium oxide (D) is not included in the colorant (G).

[0153] As the colorant (G), a pigment or a dye may be used. If necessary, a plurality of colorants may be used in combination. Incidentally, when the resulting pattern (partition ribs) is to be black, a black pigment such as carbon black may be used, or a plurality of non-black pigments may be mixed to obtain a substantially black color. When the resulting pattern (partition ribs) is to be gray, a black pigment and a white pigment may be mixed to obtain a gray color. As the pigment, it is preferable to use an organic pigment.

[0154] Specific examples of the colorant (G) include known colorants such as perylene pigments, lactam pigments, azo pigments, phthalocyanine pigments, carbon pigments such as carbon black, and metal oxide pigments such as iron black.

[0155] The white pigment is preferably at least one inorganic substance selected from the group consisting of alumina, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. These inorganic substances have a high refractive index and therefore tend to improve the light reflectivity of the partition walls that are formed. Titanium oxide is particularly preferred from the viewpoints of its high refractive index and good dispersibility in the composition.

[0156] As other color pigments, various organic pigments such as yellow, orange, blue, red, green, purple, and brown can be used. A pigment dispersion containing two or more organic pigments may also be used. Optical properties such as solubility and light-blocking properties can be controlled by adjusting the type and amount ratio of the pigments used. In particular, a combination of blue, purple, and orange is preferred from the viewpoints of compatibility and uniformity of optical density.

[0157] Examples of organic orange pigments include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, C.I. Pigment Orange 43 is preferred from the viewpoints of dispersibility and light-blocking properties.

[0158] Examples of organic blue pigments include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, and 80. Among these, C.I. Pigment Blue 60 is preferred from the viewpoints of dispersibility and light-shielding properties.

[0159] Examples of organic purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, C.I. Pigment Violet 23 is preferred from the viewpoints of dispersibility and light-blocking properties.

[0160] When a pigment is used as the colorant (G), it is preferable that the pigment has been subjected to a dispersion treatment. The pigment can be dispersed, for example, by treating the pigment, dispersant, and, if necessary, solvent using a bead mill. The type of dispersant is not particularly limited, and dispersants available from BYK Corporation can be used, for example. Furthermore, when dispersing the pigment to produce a pigment dispersion in which the pigment is dispersed in a solvent (usually an organic solvent), an alkali-soluble resin may also be used. Since pigments are difficult to remove with an alkaline developer and tend to remain as development residues, the inclusion of an alkali-soluble resin in the pigment dispersion can be expected to reduce development residues. Specific alkali-soluble resins that can be used include those specifically listed above as the alkali-soluble resin (E).

[0161] When a colorant (G) is used, only one colorant (G) may be used, or two or more colorants (G) may be used in combination. When a colorant (G) is used, the amount thereof may be appropriately adjusted taking into account the balance between obtaining the sufficient effect of using the colorant (G) and the patterning properties, developability, and strength of the resulting pattern (partition wall). Specifically, when a colorant (G) is used, the amount thereof is usually 1 to 60 mass%, preferably 3 to 55 mass%, and more preferably 5 to 50 mass%, of the total nonvolatile components of the photosensitive composition. Incidentally, when the colorant (G) has been dispersed using a dispersant or an alkali-soluble resin, the amount of the colorant (G) including the dispersant and alkali-soluble resin (excluding the volatile solvent) may be within the numerical range shown here.

[0162] (Quantum dots (H)) When the photosensitive composition of this embodiment is used, particularly for forming a photoconversion pixel, the photosensitive composition of this embodiment may further contain quantum dots (H). The quantum dots (H) are not particularly limited, and for example, those sold by reagent manufacturers can be used. In addition, for example, quantum dots described in paragraphs 0032 to 0061 of JP 2021-043445 A may be used.

[0163] When quantum dots (H) are used, only one quantum dot (H) may be used, or two or more quantum dots (H) may be used. When quantum dots are used, the amount thereof is, for example, 1 to 60 mass %, preferably 5 to 50 mass %, of the total nonvolatile components of the photosensitive composition.

[0164] (Other Components) The photosensitive composition of this embodiment may or may not contain optional components other than those described above. Examples of optional components include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion improvers, and antioxidants. Commercially available products can be used as these optional components. For example, the "KAYAMER" series manufactured by Nippon Kayaku Co., Ltd. can be used as an adhesion improver.

[0165] From the viewpoint of suppressing a decrease in sensitivity and a decrease in patterning ability, the photosensitive composition of this embodiment preferably does not contain a polymerization inhibitor, or if it contains one, it contains only a small amount. Specifically, the content of the polymerization inhibitor in the total non-volatile components of the photosensitive composition of this embodiment is preferably 0 to 1 mass%, more preferably 0 to 0.5 mass%, and even more preferably 0 to 0.05 mass%. Examples of polymerization inhibitors include stable radical compounds that capture radicals to inhibit radical polymerization. Furthermore, from the viewpoint of suppressing unintended side reactions, the photosensitive composition of this embodiment preferably does not contain a silane coupling agent, or, if it contains one, it contains only a small amount. Specifically, the content of the silane coupling agent in the total non-volatile components of the photosensitive composition of this embodiment is preferably 0 to 1 mass%, more preferably 0 to 0.5 mass%, and even more preferably 0 to 0.05 mass%.

[0166] (Solvent) The photosensitive composition of the present embodiment is generally prepared by dissolving or dispersing the above-described various components in a solvent, which generally contains an organic solvent.

[0167] Usable solvents are not particularly limited. Specific examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorine-containing solvents. These may be used alone or in combination of two or more.

[0168] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0169] Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

[0170] Examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0171] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0172] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone.

[0173] Examples of aromatic solvents include xylene and toluene.

[0174] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluorocompounds, and hexafluoroisopropyl alcohol.

[0175] In addition, for the purpose of improving the coating property, turpentine-based petroleum naphtha solvents and paraffin-based solvents, which are high-boiling weak solvents, can be used.

[0176] Among them, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate Preferably, the solvent contains at least one selected from the group consisting of dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. Furthermore, the solvent preferably contains methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone.

[0177] When a solvent is used, only one solvent may be used, or two or more solvents may be used. When a solvent is used, the amount of solvent in the photosensitive composition is preferably an amount such that the total nonvolatile component concentration becomes, for example, 5 to 85% by mass, specifically 10 to 60% by mass. By adjusting the amount of solvent, the thickness of the film to be formed can be adjusted.

[0178] <Methods and Applications of the Photosensitive Composition> A cured film can be produced using the photosensitive composition of the present embodiment by carrying out a series of steps including, for example, the following film-forming step, exposure step, development step, and heating step: A film-forming step in which the photosensitive composition of the present embodiment is applied to a substrate to form a film; An exposure step in which the film is exposed to patterned light; A development step in which the exposed film is developed; A heating step in which the developed film is heated to cure it.

[0179] The photosensitive composition of this embodiment is preferably used to form partition walls in a light-emitting element, i.e., a pattern structure for partitioning regions such as pixels in a light-emitting element or a display device. In other words, by appropriately designing the "pattern" of the patterned exposure in the exposure step in the series of steps described above, partition walls of a desired size and shape composed of a cured product of the photosensitive composition of this embodiment can be produced. Then, a light-emitting element can be produced that includes such partition walls and a light-emitting layer or a wavelength conversion layer disposed in the region (recess) partitioned by the partition walls. Furthermore, a display device can be produced using the light-emitting element.

[0180] Hereinafter, a method for producing a cured resin film (specifically, a partition wall in a light-emitting element) using the photosensitive composition of this embodiment will be described.

[0181] [Film Forming Step] In the film forming step, the photosensitive composition of the present embodiment is applied onto a substrate to form a film.

[0182] The type of substrate is not particularly limited. The substrate may be appropriately selected depending on the product to be manufactured. Examples of substrate types include silicon wafers, SiN substrates, metal substrates, glass substrates, substrates with ITO films, substrates containing metal oxides, and organic resin substrates (e.g., polyimide, polycarbonate, polyester). A layer of some kind may be formed on at least one surface of the substrate. For example, when manufacturing a light-emitting device, a first light-emitting layer may be disposed on at least one surface of the substrate. Examples of the first light-emitting layer include a layer formed from an organic electroluminescent (EL) light-emitting material, an LED light-emitting material such as a mini-LED, μ-LED, or nano-LED, or a quantum dot light-emitting material. The first light-emitting layer may be a monochromatic layer or a multi-color layer, but a monochromatic layer is preferred. Furthermore, the first light-emitting layer is preferably a monochromatic blue light-emitting layer. When a first light-emitting layer is disposed on at least one surface of the substrate, an organic or inorganic film may be disposed between the substrate and the first light-emitting layer. For example, an anti-reflective film, a multilayer resist underlayer, or a barrier layer may be provided. In addition, a driving circuit, an electrode, a planarization layer, etc. may be formed between the substrate and the first light-emitting layer. In addition, a wavelength conversion layer may be provided instead of the first light-emitting layer. Just to be clear, the substrate may not have a layer such as the first light-emitting layer formed on its surface.

[0183] The method for applying the photosensitive composition is not particularly limited. Known methods such as spin coating, bar coating, and curtain coating can be used. In some cases, an inkjet method can also be applied. When a solvent-containing photosensitive composition is used, it is preferable to dry the solvent by heating after applying the photosensitive composition. The heating temperature can be, for example, 50 to 150°C, preferably 50 to 100°C, more preferably 60 to 90°C, even more preferably 70 to 90°C, and particularly preferably 80 to 90°C. The heating time can be 60 to 200 seconds. The film thickness (dry thickness) of the film is usually 0.5 to 20 μm, preferably 1 to 15 μm.

[0184] [Exposure Step] In the exposure step, the film obtained in the film-forming step is exposed to a pattern. Specifically, light generated from a light source of an exposure device is irradiated onto the film through a photomask. The light can be ultraviolet light, gamma rays, X-rays, etc. Due to the availability of light sources, ultraviolet light (particularly g-rays, i-rays, etc.) is mainly used as the light. The exposure dose is not particularly limited, but is usually 1 to 200 mJ / cm. ２ , preferably 10 to 100 mJ / cm ２ After the exposure and before the development step described below, a heat treatment may or may not be carried out.

[0185] In the development step, the film after the exposure step is typically developed using a developer, which usually dissolves the unexposed areas in the film, thereby obtaining a pattern (partition walls).

[0186] An alkaline aqueous solution is preferably used as the developer. Specifically, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, etc. can be used. As the developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferred in view of its good developability and long track record of use in the field of photosensitive compositions. The concentration of the TMAH aqueous solution is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass. Incidentally, a developer containing an organic solvent as its main component may be used in some cases.

[0187] As the developing method, known methods can be used, such as a dipping method, a puddle method, a spray method, etc. The developing time (the time during which the developer is in contact with the film) is preferably from 10 seconds to 3 minutes, and more preferably from 30 seconds to 2 minutes.

[0188] After the development treatment, if necessary, a step of washing the pattern with deionized water etc. The washing time is preferably from 10 seconds to 3 minutes, more preferably from 30 seconds to 2 minutes.

[0189] [Heating Step] In the heating step, the developed film is heated. This allows the remaining reactive groups in the pattern obtained in the development step to react as much as possible, thereby hardening the film. In the heating step, the developed film is heated, for example, at 50 to 250°C, preferably 50 to 230°C, more preferably 60 to 220°C, even more preferably 70 to 200°C, particularly preferably 50 to 150°C, and especially preferably 50 to 100°C. By not raising the heating temperature too high, it is easy to suppress alteration and deterioration of the dye and other materials in the light-emitting element. The heating time is, for example, 10 minutes to 3 hours, preferably 15 minutes to 1 hour.

[0190] [Optional Steps After Heating Step] The cured film obtained in the heating step may be subjected to UV ozone treatment or oxygen plasma treatment, which can remove organic matter remaining in the recesses of the pattern (cured film) and reduce uneven wetting of the dropped ink during the ink dropping process described below.

[0191] To obtain a light-emitting element, a second light-emitting layer formation step is preferably performed, in which a second light-emitting layer that emits light using light from the first light-emitting layer as excitation light is formed in the recesses of the pattern (cured film), i.e., in the areas partitioned by the partition walls. The second light-emitting layer preferably contains a conventionally known material, such as a quantum dot light-emitting material. As described in the Background Art section, the second light-emitting layer can be formed, for example, by depositing ink droplets into the recesses of the pattern (cured film) using an inkjet method and then drying and / or solidifying the ink. In other words, a light-emitting element may be obtained by depositing ink for forming the second light-emitting layer droplets into the recesses of the pattern (cured film) using an inkjet method.

[0192] Alternatively, in order to obtain a light-emitting element that emits RGB light, ink containing a red, green, or blue dye (typically, a liquid in which a pigment is dispersed) may be dropped into the recesses of the pattern (cured film), i.e., the areas defined by the partition walls, and then the ink may be dried and / or solidified.

[0193] (Additional explanation when the photosensitive composition contains quantum dots (H)) By using a photosensitive composition containing quantum dots (H) and carrying out, for example, the above-mentioned film formation process, exposure process, development process, heating process, etc., it is possible to form photoconversion pixels composed of a cured product of the photosensitive composition. In addition, it is possible to manufacture a color filter including the photoconversion pixels. Furthermore, it is possible to manufacture an image display device including the color filter.

[0194] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0195] The embodiments of the present invention will be described in detail based on examples and comparative examples. It should be noted that the present invention is not limited to the examples. In the following, "PGMEA" is an abbreviation for propylene glycol monomethyl ether acetate.

[0196] <Preparation of Raw Materials> The following raw materials were prepared.

[0197] (Compound (A) Having an Ethylenic Carbon-Carbon Double Bond) A-TMM-3LM-N: manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of tetramethylolmethane triacrylate and tetramethylolmethane tetraacrylate, having the following structure:

[0198]

[0199] RP-1040: Ethoxylated pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd., structure shown below

[0200]

[0201] (Thiol Compound (B)) PEMP: manufactured by SC Organic Chemicals Co., Ltd., pentaerythritol tetrakis(3-mercaptopropionate), a primary thiol having the following structure:

[0202]

[0203] Karenz-MTPE1: manufactured by Resonac, pentaerythrityl tetramercaptobutyrate, a secondary thiol having the following structure

[0204]

[0205] (Photoradical initiator (C)) OXE01: 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime), manufactured by BASF, structure shown below.

[0206]

[0207] Ominirad 819: manufactured by IGM Resins, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, structure shown below

[0208]

[0209] (Titanium oxide (D), or stabilizer for comparative examples (polymerization inhibitor, etc.)) Titanium oxide 1: NX-501, titanium oxide (rutile type) pigment-containing dispersion, pigment content: 73% by mass, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., D ５０ : 270 nm 4-Methoxyphenol: manufactured by Tokyo Chemical Industry Co., Ltd. 4-Methoxy-1-naphthol: manufactured by Tokyo Chemical Industry Co., Ltd. 1,2,3-Trihydroxybenzene: manufactured by Tokyo Chemical Industry Co., Ltd. 3,3'-thiobispropionate ditridecyl: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Acrylic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

[0210] (Alkali-soluble resin (E)) ZAR-2050H: Special BIS-A type epoxy acrylate manufactured by Nippon Kayaku Co., Ltd., having the following structure:

[0211]

[0212] (Liquid Repellent (F)) A fluororesin synthesized as follows was used as the liquid repellent (liquid repellent 1). Synthesis of Liquid Repellent Precursor 1: In a 300 mL glass flask equipped with a stirrer, 0.2 g (0.001 mol) of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd., hereinafter referred to as BTFBE), 1.8 g (0.01 mol) of 4-acetoxystyrene (obtained from Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 2-(perfluorohexyl)-1,3-butadiene (obtained from Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St) and 1.8 g (0.01 mol) of 4-acetoxystyrene (obtained from Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St) were added at room temperature (approximately 20°C). 43.2 g (0.12 mol) of ethyl methacrylate (obtained from Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C6F), 0.6 g (0.005 mol) of methacrylic acid (Wako Pure Chemical Industries, Ltd., hereinafter referred to as MAA), 24.3 g (0.22 mol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HEMA), and 102.8 g of PGMEA were added. Then, 1.38 g (0.01 mol) of 2,2'-azobis(2-methylbutyronitrile) (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was added to the flask, and after degassing with stirring, the flask was purged with nitrogen gas, and the internal temperature was raised to 79 ° C. and allowed to react overnight. After completion of the reaction, the mixture was allowed to cool, and then 300 g of n-heptane was added dropwise to the reaction system. As a result, 58.2 g of liquid repellent precursor 1 was obtained as a white solid in a yield of 83%.

[0213] ・ １３ C-NMR measurement results: The composition ratio of each structural unit of liquid repellent precursor 1, expressed as a molar ratio, was: structural unit by BTFBE: structural unit by p-AcO-St: improved unit by MA-C6F: structural unit by MAA: structural unit by HEMA = 1:10:30:5:54. For reference, the structure of liquid repellent precursor 1 is shown below.

[0214]

[0215] Synthesis of Liquid Repellent 1: 6.4 g of Liquid Repellent Precursor 1 (hydroxyl group equivalent: 0.02 mol), 0.07 g of triethylamine (obtained from Tokyo Chemical Industry Co., Ltd.) (hydroxyl group equivalent: 0.001 mol), and 50 g of PGMEA were placed in a 200 mL glass flask equipped with a stirrer. Then, 1.51 g of Karenz AOI (obtained from Showa Denko K.K., 2-acryloyloxyethyl isocyanate) (hydroxyl group equivalent: 0.02 mol) was added to the flask, and the mixture was allowed to react at 60°C for 20 hours. After allowing the reaction solution to cool, 200 g of n-heptane was added to the reaction solution to precipitate a precipitate. In this way, 6.4 g of Liquid Repellent 1 was obtained as a white solid in an 81% yield.

[0216] ・ １３ C-NMR measurement results: In Liquid Repellent 1, the amount of acrylic acid derivative introduced from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 4:1 in molar ratio. Furthermore, it was confirmed that the composition ratio of each structural unit that does not react with the crosslinking group site (structural unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MAA) was unchanged from that of Liquid Repellent Precursor 1 used (the same as before the introduction of crosslinking groups). For reference, the structure of Liquid Repellent 1 is shown below.

[0217]

[0218] (Colorant (G)) Color pigment dispersion 1: Lactam black pigment consisting of the following compound, pigment content relative to total solid content: 75% by mass, D ５０ : 300 nm

[0219]

[0220] Color pigment dispersion 2: Prepared as follows, pigment content relative to total solids: 66% by mass, D ５０ The pigment, dispersant, alkali-soluble resin, and solvent shown in the table below were mixed in the mass ratio shown. This solution was dispersed in a bead mill using 0.5 mmφ zirconia beads at 25°C for 12 hours. After the dispersion treatment was completed, the beads were removed by filtration to obtain Color Pigment Dispersion 2.

[0221]

[0222] (Other ingredients) Adhesion imparting agent: PM-21, manufactured by Nippon Kayaku, phosphate ester compound

[0223] <Preparation of Photosensitive Composition> Each component was placed in a light-shielding bottle so that the solid content of each component in the total non-volatile components was the ratio shown in the table below. Furthermore, the concentration was adjusted using PGMEA. The contents of the light-shielding bottle were thoroughly stirred to dissolve or disperse each component, thereby preparing a photosensitive composition.

[0224] <Evaluation of Storage Stability> Each photosensitive composition shown in the table below was placed in an oven (EYELA, manufactured by Tokyo Rikakiki Co., Ltd., Model No. VOS-201SD). The temperature was set to 30°C or 100°C and kept warm. The photosensitive composition was removed from the oven after 1, 4, or 12 weeks when the temperature was set to 30°C, and after 1, 5, or 15 hours when the temperature was set to 100°C. The degree of curing of the removed photosensitive composition was evaluated using a Komagome pipette (capacity: 10 mL, tip outer diameter: φ3.7 mm, top diameter: φ12 mm, total length: 280 mm). Specifically, the evaluation was based on the following criteria: Not cured: The photosensitive composition could be sucked up to the full capacity (10 mL) of the Komagome pipette. Cured: Due to solidification or an increase in viscosity, the photosensitive composition could not be sucked up to the full capacity (10 mL) of the Komagome pipette.

[0225] <Evaluation of Patterning Properties> (Substrate Preparation) A non-alkali glass substrate (0.7 mm thick x 100 Φ) was washed with ultrapure water and then with acetone. Thereafter, the substrate was subjected to UV ozone treatment for 2 minutes using a UV ozone treatment device (manufactured by Sen Special Light Sources Co., Ltd., Model No. PL17-110).

[0226] (Formation of Resin Film) Each of the photosensitive compositions of Examples 1 to 9 and Comparative Example 8, which had been stored at 100°C for 5 hours in the <Storage Stability Test>, was applied onto the substrate after the UV ozone treatment using a spin coater at a rotation speed of 500 rpm, and heated on a hot plate at 80°C for 90 seconds. In this way, a resin film was formed.

[0227] (Exposure, Development, etc.) The resin film was exposed to ghi rays (wavelengths of 365, 405, and 436 nm) through a 210 ppi mask at 90 to 150 mJ / cm using a manual exposure machine (manufactured by SCREEN Finetech Solutions, model number MA-1400). ２ (Illuminance 6mW / cm ２ ) was irradiated. Thereafter, using a developing machine (manufactured by Mikasa Co., Ltd., model number AD-3000), the film was developed with a 0.04 mass % KOH aqueous solution for 60 seconds, and then shower-washed with distilled water for 10 seconds. Further, using a hot plate, a heat treatment was performed at 80°C for 15 minutes. In this manner, a pattern (a structure simulating a partition wall for partitioning regions such as pixels in a light-emitting element or display device) was obtained.

[0228] The obtained pattern was observed using a laser microscope. The openings of the pattern (210 ppi) were observed, and the occurrence of distortion and residue in the partition wall portion was evaluated according to the following criteria: Good: No pattern distortion or residue. Slightly poor: No pattern distortion, but residue present. Poor: Pattern distortion present.

[0229] The various information is summarized in the table below.

[0230]

[0231] As shown in the table above, the photosensitive compositions of Examples 1 to 10, which contained titanium oxide in an amount of 5% by mass or more of the total non-volatile components, showed good evaluation results for storage stability. Furthermore, the photosensitive compositions of Examples 1 to 10 also showed good evaluations for patterning properties. In other words, the photosensitive compositions of this embodiment had good storage stability and also good patterning properties. Incidentally, the difference between Examples 1 to 9 and 10 is whether a primary thiol or a secondary thiol was used as the thiol compound (B), and both showed good storage stability and patterning properties. However, in Examples 1 to 9, the thiol compound (B) was 90 mJ / cm ２ In Example 10, a sufficiently cured pattern was obtained with a low exposure dose of 150 mJ / cm. ２ An exposure dose of 1000 nm was required.

[0232] The photosensitive compositions of Comparative Examples 1 to 8, which contained no titanium oxide or had a small amount of titanium oxide compared to Examples 1 to 10, had poorer storage stability than Examples 1 to 10. Furthermore, even the photosensitive composition of Comparative Example 8, which had relatively good storage stability, had inferior patterning properties compared to Examples 1 to 10.

[0233] <Additional Evaluation: Comparison with Conventional Polymerization Inhibitors, etc.> The use of titanium oxide is particularly superior, as shown by comparison with conventional polymerization inhibitors, etc. First, the photosensitive compositions shown in the table below were prepared. Then, as described in the above <Evaluation of Storage Stability>, the degree of curing of the photosensitive compositions after storage at 100°C for 5 hours was evaluated. Furthermore, as described in the above <Evaluation of Patterning Properties>, patterns (structures) resembling partition walls were formed and evaluated. However, the evaluation criteria were as follows: Good: No pattern defects Slightly poor: Part of the pattern peeled off Poor: Complete peeling

[0234] The composition and evaluation results are summarized in the table below.

[0235]

[0236] As shown in the table above, when conventional polymerization inhibitors or the like were used as stabilizers, the patterning properties were worse than when titanium oxide was used. From this result, it is clear that as long as conventional polymerization inhibitors or the like are used, it is difficult to achieve both good storage stability and other properties such as patterning properties.

[0237] This application claims priority based on Japanese Patent Application No. 2024-129703, filed on August 6, 2024, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A photosensitive composition comprising: (A) a compound having an ethylenic carbon-carbon double bond; (B) one or more thiol compounds selected from the group consisting of thiols and thiol precursors; (C) a photoradical initiator; and (D) titanium oxide, wherein the proportion of the titanium oxide (D) in all nonvolatile components is 5 mass% or more.

2. The photosensitive composition according to claim 1, wherein the ratio of the thiol compound (B) to all nonvolatile components is 5% by mass or more.

3. The photosensitive composition according to claim 1 or 2, wherein the ratio of said titanium oxide (D) to all non-volatile components is 30 mass % or less.

4. A photosensitive composition according to claim 1 or 2, wherein the thiol compound (B) comprises at least one selected from the group consisting of primary thiols and compounds that generate primary thiols upon physical stimulation or chemical action.

5. The photosensitive composition according to claim 1 or 2, wherein the titanium oxide (D) has a median diameter D ５０ The photosensitive composition is in the form of a powder having a size of 50 to 300 nm.

6. The photosensitive composition according to claim 1 or 2, wherein the titanium oxide (D) comprises rutile-type titanium oxide.

7. The photosensitive composition according to claim 1 or 2, wherein the content of the polymerization inhibitor in all nonvolatile components is 0 to 1% by mass.

8. The photosensitive composition according to claim 1 or 2, wherein the content of the silane coupling agent in the total non-volatile components is 0 to 1 mass %.

9. The photosensitive composition according to claim 1 or 2, further comprising an alkali-soluble resin (E).

10. The photosensitive composition according to claim 1 or 2, further comprising a liquid repellent (F).

11. The photosensitive composition according to claim 1 or 2, further comprising a colorant (G).

12. The photosensitive composition according to claim 1 or 2, which is used to form a partition wall in a light-emitting device.

13. The photosensitive composition according to claim 1 or 2, further comprising quantum dots (H), which is used to form photoconversion pixels.

14. A method for producing a resin cured film, comprising: a film-forming step of applying the photosensitive composition according to claim 1 or 2 onto a substrate to form a film; an exposure step of pattern-exposing the film; a development step of developing the exposed film; and a heating step of heating and curing the developed film.

15. A method for producing a cured resin film according to claim 14, wherein in the heating step, the developed film is heated at 50 to 150°C.

16. A method for producing a cured resin film according to claim 14, wherein in the heating step, the developed film is heated at 50 to 100°C.

17. A method for producing a cured resin film according to claim 14, wherein the applied photosensitive composition is heated at 50 to 150°C in the film-forming step.

18. A partition wall made of a cured product of the photosensitive composition according to claim 1 or 2.

19. The partition wall according to claim 18, which is for a light emitting element.

20. A light-emitting element comprising the partition wall according to claim 18 and a light-emitting layer or a wavelength conversion layer disposed in an area defined by the partition wall.

21. A display device comprising the light-emitting element according to claim 20.

22. A photoconversion pixel made of a cured product of the photosensitive composition according to claim 13.

23. A color filter comprising the photoconversion pixel of claim 22.

24. An image display device comprising the color filter according to claim 23.

Images