Photosensitive composition, method for producing cured film, partition wall, light-emitting element, and display device

Abstract

This photosensitive composition comprises (A) a compound having an ethylenic carbon-carbon double bond, (B) one or more thiol-based compounds selected from the group consisting of thiols and thiol precursors, (C) a photoradical initiator, and (D) a disulphide compound.

Description

Photosensitive composition, method for producing cured film, partition wall, light-emitting element, and display device

[0001] The present invention relates to a photosensitive composition, a method for producing a cured film, a partition wall, a light-emitting element, and a display device.

[0002] Photosensitive compositions are industrially important and have a wide range of applications, so various improvements are being continuously investigated.

[0003] One application of photosensitive compositions is their use in forming partition walls (banks) in display devices. When manufacturing light-emitting elements in display devices such as organic electroluminescent (EL) displays, micro LED displays, and quantum dot displays, a known method for forming an organic layer with light-emitting properties involves, for example, dropping ink into recesses of a textured pattern formed on a substrate using an inkjet method, followed by drying and / or solidifying the ink. Here, the "textured pattern" is referred to as a partition wall (bank). The partition wall acts as a barrier to prevent ink droplets from mixing when dropped into the recesses of the pattern. The partition wall preferably has a moderate ink-repelling property. This is to prevent ink dropped into one recess from "creeping" along the side of the partition wall and seeping into an adjacent recess. The partition wall can be formed by photolithography using a photosensitive composition.

[0004] Patent Document 1 describes a negative photosensitive resin composition that contains an alkali-soluble resin or an alkali-soluble monomer having an ethylenic double bond, a photopolymerization initiator, a thiol compound having three or more mercapto groups in one molecule, and an ink repellent agent, as a composition that can be preferably used for forming partition walls of optical elements.

[0005] Patent Document 2 describes a photosensitive composition containing at least an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and at least one compound having two or more chain-transferable substituents (specifically, a thiol compound). However, Patent Document 2 does not specifically mention the formation of partition walls of optical elements.

[0006] International Publication No. 2014 / 084279 Japanese Patent Application Laid-Open No. 2006-285174

[0007] In practice, photosensitive compositions are sometimes required to have good storage stability, i.e., to have little change in performance over time. However, based on the findings of the present inventors, there is still room for improvement in the storage stability of conventional photosensitive compositions.

[0008] The present invention has been made in view of the above circumstances, and one of the objects of the present invention is to provide a photosensitive composition having good storage stability.

[0009] The present inventors have completed the invention provided below and solved the above problems.

[0010] 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) a disulfide compound. 2. The photosensitive composition according to 1., wherein the proportion of the disulfide compound (D) in all nonvolatile components is 1 to 30,000 ppm. 3. The photosensitive composition according to 1. or 2., wherein the amount of the disulfide compound (D) is 0.01 to 40 parts by mass per 100 parts by mass of the thiol compound (B). 4. The photosensitive composition according to any one of 1. to 3., wherein the disulfide compound (D) comprises a polymer of the thiol compound (B). 5. 1. to 4. 5. The photosensitive composition according to any one of 1. to 4., wherein the amount of the thiol compound (B) in all non-volatile components is 0.1 to 10 mass %. 6. The photosensitive composition according to any one of 1. to 5., further comprising an alkali-soluble resin (E). 7. The photosensitive composition according to any one of 1. to 6., further comprising a fluorine-containing resin (F). 8. The photosensitive composition according to any one of 1. to 7., further comprising a colorant (G). 9. The photosensitive composition according to any one of 1. to 8., wherein the viscosity of the photosensitive composition measured using a Brookfield viscometer is η ０ The viscosity of the photosensitive composition measured using a Brookfield viscometer after storing the photosensitive composition at 40°C for 7 days is defined as η １ When this is done, (|η １ -η ０ | / η ０) × 100(%) is 15% or less. 10. The photosensitive composition according to any one of 1. to 9., which is used for forming a partition wall in a light-emitting device. 11. A method for producing a cured film, comprising: a film-forming step of applying the photosensitive composition according to any one of 1. to 10. on a substrate to form a film; an exposure step of patternwise exposing the film; a development step of developing the exposed film; and a heating step of heating and curing the developed film. 12. A partition wall composed of a cured product of the photosensitive composition according to any one of 1. to 10.. 13. The partition wall according to 12., which is for a light-emitting device. 14. A light-emitting device comprising the partition wall according to 12. or 13., and a light-emitting layer or a wavelength conversion layer arranged in a region partitioned by the partition wall. 15. A display device comprising the light-emitting device according to 14.

[0011] According to the present invention, a photosensitive composition having good storage stability is provided.

[0012] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the notation "X to Y" in the description of a numerical range means X or more and Y or less, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less." In the notation of groups (atomic groups) in this specification, notations that do not specify whether they are substituted or unsubstituted include both unsubstituted and substituted groups. For example, the term "alkyl group" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, the notation "(meth)acrylic" 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.

[0013] <Photosensitive Composition> The photosensitive composition of the present embodiment contains: (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) a disulfide compound.

[0014] Disulfide compound (D) has been known as a chain transfer agent in radical polymerization reactions, and it is generally recognized that it does not terminate the polymerization reaction itself. However, the present inventors have unexpectedly found that disulfide compound (D) appears to enhance the storage stability of photosensitive compositions. More specifically, the mechanism behind this can be considered as follows.

[0015] Radicals unintentionally generated in the photosensitive composition, particularly radicals generated by unintentional decomposition of the photoradical initiator (C), react with the thiol compound (B) to generate S radicals. The generated S radicals react with the disulfide compound (D) faster than they react with the compound (A) having an ethylenic carbon-carbon double bond, generating a different S radical. The further reaction of these radicals with the disulfide compound (D) inhibits their reaction with the compound (A) having an ethylenic carbon-carbon double bond. It is assumed that a certain proportion of the generated radicals are deactivated. It should be noted that the above mechanism is merely speculation, and the present invention is not limited by the description of the above mechanism.

[0016] The photosensitive composition will be further described below.

[0017] (Compound (A) Having an Ethylenic Carbon-Carbon Double Bond) The photosensitive composition of the present embodiment contains a compound (A) having an ethylenic carbon-carbon double bond. In this specification, the compound (A) having an ethylenic carbon-carbon double bond may be simply referred to as compound (A).

[0018] 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. Conjugation-stabilized double bonds such as the double bond of a benzene ring do 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.

[0019] 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.

[0020] 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.

[0021] Specific examples of the compound (A) include the following: Of course, the compound (A) is not limited to these.

[0022] 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.

[0023] 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%.

[0024] (Thio-based compound (B)) The photosensitive composition of the present embodiment contains one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors. In this specification, 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).

[0025] 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.

[0026] Specific examples of the thiol in the thiol compound (B) include those represented by the following general formula (b).

[0027]

[0028] 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.

[0029] 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.

[0030] 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.

[0031] Commercially available thiols in the thiol compound (B) include, for example, the "Karens" 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. Generally, primary thiols are more reactive and may be more advantageous in terms of low-temperature curing. However, as shown in the examples below, it is possible to obtain satisfactory results even with secondary thiols. Incidentally, secondary thiols may suppress the reactivity of the thiol group due to steric hindrance, potentially improving the stability of the composition.

[0032] 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 formed into a salt. Thiol precursors are described, for example, in JP-A-2004-517979.

[0033] 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.

[0034] 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).

[0035] The content of the thiol compound (B) is not particularly limited, but in one embodiment, it is, for example, 0.1 to 10 mass %, specifically 0.5 to 8 mass %, more specifically 1 to 5 mass %, based on the total nonvolatile components of the photosensitive composition. Having the content of the thiol compound (B) within the numerical range shown here is preferable because it further improves the storage stability of the photosensitive composition. Furthermore, the content of the thiol compound (B) is, for example, 0.2 to 25 mass parts, specifically 1 to 20 mass parts, more specifically 2 to 15 mass parts, relative to 100 mass parts of compound (A). Incidentally, 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 compound (A).

[0036] In another embodiment, the content of the thiol-based compound (B) is typically 10 to 70 mass%, preferably 15 to 60 mass%, and more preferably 20 to 55 mass% of the total nonvolatile components of the photosensitive composition. The content of the thiol-based compound (B) is, for example, 30 to 80 mass parts, specifically 30 to 70 mass parts, and more specifically 35 to 70 mass parts, per 100 mass parts of compound (A). When the thiol-based compound (B) is used in this amount, the photosensitive composition is believed to cure primarily through the thiol-ene reaction, which is known as a bond-forming reaction between a thiol and an alkene. Depending on the ratio of compound (A) to thiol-based compound (B), both the radical polymerization reaction of compound (A) and the thiol-ene reaction may occur.

[0037] (Photoradical initiator (C)) The photosensitive composition of the present embodiment contains a photoradical initiator (C). As the photoradical initiator (C), any initiator that generates radicals when irradiated with light (typically ultraviolet light such as i-line) can be used without any particular limitation.

[0038] Specific examples of the photoradical initiator (C) include an intramolecular cleavage type in which an intramolecular bond is cleaved by absorption of electromagnetic waves or an electron beam to generate a radical, and a hydrogen abstraction type in which a radical is generated by using a hydrogen donor such as a tertiary amine or an ether in combination. In this embodiment, any of these may be used. Of course, photoradical initiators other than these may also be used.

[0039] Specific examples of the photoradical initiator (C) include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, and oxime ester-based photoradical initiators.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] Specific examples of the acylphosphine oxide initiator include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0044] Specific examples of the quinone initiator include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0045] 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.

[0046] Specific examples of oxime ester initiators include 1-[4-(phenylthio)phenyl]-1,2-octadione-2-(o-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(o-acetyloxime)].

[0047] Among commercially available photoradical initiators, preferred ones include BASF's product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04, Darocur 1173, and Lucirin TPO; and Tronly's product name: TR-PBG-305.

[0048] 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 sensitivity and resolution. 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.

[0049] (Disulfide Compound (D)) The photosensitive composition of this embodiment contains a disulfide compound (D). As described above, the disulfide compound (D) is considered to be particularly related to the improvement of storage stability.

[0050] There are no particular limitations on the disulfide compound (D) that can be used. Compounds containing one or more disulfide bonds in one molecule can be used without particular limitations. Incidentally, when a compound has both a thiol group and a disulfide bond, the compound is classified as a disulfide compound (D).

[0051] Specific examples of the disulfide compound (D) include: dialkyl disulfides such as dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-isopropyl disulfide, di-n-butyl disulfide, di-isobutyl disulfide, di-sec-butyl disulfide, di-tert-butyl disulfide, di-n-pentyl disulfide, di-tert-pentyl disulfide, diisopentyl disulfide, di-n-heptyl disulfide, di-tert-octyl disulfide, di-n-decyl disulfide, and dicyclohexyl disulfide; and disulfides having an aromatic group (diaryl disulfides) such as dibenzyl disulfide, diphenyl disulfide, di-p-tolyl disulfide, and 5,5'-dithiobis(2-nitrobenzoic acid). Disulfides having a heterocyclic group such as 2,2'-dipyridyl disulfide, 4,4'-dipyridyl disulfide, 2,2'-dithiobis(5-nitropyridine), 6,6'-dithiodinicotinic acid, and 2,2'-dipyrimidinyl disulfide.

[0052] As the disulfide compound (D), a known or commercially available product may be used. Alternatively, the disulfide compound (D) may be synthesized by oxidizing a thiol compound under appropriate conditions. The disulfide compound (D) can be synthesized by oxidizing a known or commercially available thiol with an appropriate oxidizing agent. Just to be clear, the synthesis of a disulfide by oxidation of a thiol is an elementary organic chemistry reaction.

[0053] The disulfide compound (D) may also be a polymer (e.g., a dimer) of the thiol compound (B). Specifically, the photosensitive composition of this embodiment may contain a thiol compound (B) having a specific structure and a disulfide compound (D) that is a polymer of the thiol compound (B). In this case, the thiol compound (B) and the disulfide compound (D) are structurally similar, which is considered preferable in terms of the uniformity of the composition and the compatibility of the components. Furthermore, this structural similarity may facilitate smoother transfer of radicals between the thiol compound (B) and the disulfide compound (D). Just to be clear, the disulfide compound (D) does not necessarily have to contain a polymer of the thiol compound (B).

[0054] The disulfide compound (D) is usually a low molecular weight compound. The disulfide compound (D) is usually not a polymer having a periodic unit structure. The upper limit of the molecular weight of the disulfide compound (D) is not particularly limited, but the upper limit is, for example, 3,000 or less, preferably 2,000 or less, and more preferably 1,500 or less. The lower limit of the molecular weight of the disulfide compound (D) is also not particularly limited, but the lower limit is, for example, 94 (the molecular weight of dimethyl disulfide).

[0055] The photosensitive composition of the present embodiment may contain only one disulfide compound (D), or may contain two or more disulfide compounds (D).

[0056] The proportion of the disulfide compound (D) in all nonvolatile components of the photosensitive composition is preferably 1 to 30,000 ppm, more preferably 5 to 25,000 ppm, and even more preferably 10 to 20,000 ppm. When the proportion of the disulfide compound (D) is 1 ppm or more, the effect of improving storage stability can be sufficiently achieved. An upper limit may be set in consideration of the balance with other components. In that case, the upper limit mentioned here may be used.

[0057] Furthermore, the amount of the disulfide compound (D) relative to 100 parts by mass of the thiol compound (B) is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.1 to 20 parts by mass. When this amount is 0.01 part by mass or more, the effect of improving storage stability is easily achieved. Furthermore, when this amount is 40 parts by mass or less, the effect of improving storage stability can be achieved while suppressing deterioration in performance other than storage stability, such as sensitivity. Incidentally, assuming the above-mentioned estimated mechanism, the disulfide compound (D) accepts radicals from the radicalized thiol compound (B). Therefore, the amount of the disulfide compound (D) relative to 100 parts by mass of the thiol compound (B) described above can also be interpreted as representing the quantitative ratio of the thiol compound (B) to the disulfide compound (D) that is suitable for efficient transfer of radicals from the thiol compound (B) to the disulfide compound (D).

[0058] Generally, in photosensitive compositions, sensitivity and storage stability are in a trade-off relationship. However, in this embodiment, by setting the amount of disulfide compound (D) to the aforementioned ratio, a good balance between sensitivity and storage stability is achieved. Although the details of this are unclear, as mentioned above, it is possible that a presumed mechanism in which the reaction of compound (A) is suppressed by a radical reaction mediated by the thiol-based compound (B) is involved. Specifically, it is possible that a mechanism in which the disulfide compound (D) does not directly capture radicals generated by unintended decomposition of the photoradical initiator (C), but rather the generated radicals first pass through the thiol-based compound (B) and then propagate to the disulfide compound (D) is involved. Because the disulfide compound (D) does not directly capture radicals generated from the photoradical initiator (C), radicals generated during exposure are less likely to be deactivated, potentially suppressing the impact on sensitivity.

[0059] (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 (partition wall) using an alkali 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. In this specification, a resin that has a fluorine atom and is alkali-soluble is generally classified as a fluorine-containing resin (F) described below. In other words, the alkali-soluble resin (E) generally does not have a fluorine atom.

[0060] 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.

[0061] 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):

[0062]

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Epoxy (meth)acrylate resins having a structural unit represented by general formula (e) are available from, for example, Nippon Kayaku Co., Ltd.

[0068] 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.

[0069] 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.

[0070] 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).

[0071] 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.

[0072] 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.

[0073] (Fluorine-Containing Resin (F)) The photosensitive composition of this embodiment preferably contains a fluorine-containing resin (F). By forming a pattern (partition wall) having concaves and convexes using a photosensitive composition containing a fluorine-containing resin (F), the resulting pattern (partition wall) becomes more likely to repel ink for forming an organic layer. This contributes to preventing ink dropped into a certain depression from "crawling" along the side surface of the depression and entering an adjacent depression. In other words, it is possible to prevent unintended mixing of dye between pixels.

[0074] There are no particular restrictions on the fluorine-containing resin (F) that can be used. Preferred fluorine-containing resins (F) that can be used are described below. The fluorine-containing resin (F) preferably has a structure represented by the following general formula (1), and more preferably has a structure represented by the following general formula (2).

[0075]

[0076] 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; ２represents 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]

[0078] 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.

[0079] 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.

[0080] 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.

[0081] Preferred specific structures of the structural units include the structures described in paragraphs 0060 to 0061 of WO 2021 / 235541.

[0082] The content of the structural unit represented by general formula (2) in the fluorine-containing resin (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 solubility in solvents, resistance to various treatments in the production of light-emitting elements, and the like.

[0083] The fluorine-containing resin (F) may contain a structure represented by the following general formula (3).

[0084]

[0085] In general formula (3), R ３ , R ４ each independently represents a hydrogen atom or a methyl group.

[0086] 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.

[0087] 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

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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:

[0093] 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:

[0094] In the general formula (3), Y １ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0095] 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.

[0096] Specific preferred examples of the structure represented by general formula (3) include the structures described in paragraphs 0081 to 0084 of WO 2021 / 235541.

[0097] The content of the structural unit represented by general formula (3) in the fluorine-containing resin (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 solubility in solvents, resistance to various treatments in the production of light-emitting elements, and the like.

[0098] The fluorine-containing resin (F) may contain a structure represented by the following general formula (4).

[0099]

[0100] In general formula (4), R ５ , R ６ each independently represents a hydrogen atom or a methyl group.

[0101] 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.

[0102] 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

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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:

[0108] 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 particularly preferably —C(CH ２ -) ２ CH ３ The tetravalent linking group A3 can be C(CH ２ -) ４ Examples include:

[0109] 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—.

[0110] 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.

[0111] 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.

[0112] Specific preferred examples of the structure represented by general formula (4) include the structures described in paragraphs 1005 to 0109 of WO 2021 / 235541.

[0113] The content of the structural unit represented by general formula (4) in the fluorine-containing resin (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 a substrate.

[0114] The fluorine-containing resin (F) may contain a structural unit represented by general formula (5).

[0115]

[0116] In general formula (5), R ７ represents a hydrogen atom or a methyl group.

[0117] 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.

[0118] 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.

[0119] 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):

[0120]

[0121] In general formula (5-1), R ９ is R in general formula (5). ７ is synonymous with.

[0122] In the general formula (5-1), X is a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

[0123] 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.

[0124] 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.

[0125] The content of the structural unit represented by general formula (5) in the fluorine-containing resin (F) may be appropriately determined taking into consideration the ease with which the resin repels ink when formed into a pattern (partition wall), the ease with which the resin 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 fluorine-containing resin (F) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0126] The fluorine-containing resin may contain a structure represented by the following general formula (6).

[0127]

[0128] In general formula (6), R １０represents a hydrogen atom or a methyl group.

[0129] 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.

[0130] Specific preferred examples of the structure represented by general formula (6) include the structures described in paragraphs 0137 to 0138 of WO 2021 / 235541.

[0131] The content of the structural unit represented by general formula (6) in the fluorine-containing resin (F) is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 20 to 40 mass%, in consideration of sufficiently obtaining the effect based on the structural unit represented by general formula (6) and of solvent solubility.

[0132] In the general formula (6), B １ is a hydroxy group or a carboxyl group, the structural unit represented by formula (6) has solubility in an alkaline developer. Therefore, when particularly good alkaline developability is desired, the fluorine-containing resin (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.

[0133] The fluorine-containing resin (F) may contain a structure represented by the following general formula (7):

[0134]

[0135] In general formula (7), R １３ represents a hydrogen atom or a methyl group.

[0136] In 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

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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)CH２ 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.

[0141] 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:

[0142] 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.

[0143] In the general formula (7), Y４ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0144] In general formula (7), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0145] 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.

[0146] 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.

[0147] Specific preferred examples of the structure represented by general formula (7) include the structure described in paragraph 0156 of WO 2021 / 235541.

[0148] The weight average molecular weight of the fluororesin (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 molecular weight of the fluororesin (F) may make it possible to increase the strength of the pattern (partition walls) to be formed or to increase the solubility in solvents and thereby improve coatability.

[0149] The polydispersity (Mw / Mn) of the fluorine-containing resin (F) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, particularly preferably from 1.01 to 3.00.

[0150] The fluorine-containing resin (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.

[0151] The fluorine content of the fluorine-containing resin (F) is preferably 20 to 50% by mass, more preferably 25 to 40% by mass. When the fluorine content is within this range, the fluorine-containing resin (F) is easily dissolved in a solvent. Furthermore, when the fluorine content of the fluorine-containing resin (F) is within this range, a pattern (partition wall) having excellent liquid repellency is easily obtained. The fluorine content of the fluorine-containing resin (F) can be measured, for example, in accordance with the description in paragraph 0174 of WO 2021 / 235541.

[0152] When a fluorine-containing resin (F) is used, only one fluorine-containing resin (F) may be used, or two or more fluorine-containing resins (F) may be used. In order to strike a balance between sufficient liquid repellency of the resulting pattern (partition wall) and good alkali developability, the amount of the fluorine-containing resin (F), when used, is usually 0.1 to 10 mass %, preferably 0.1 to 8 mass %, and more preferably 0.5 to 5 mass %, of the total non-volatile components of the photosensitive composition.

[0153] In addition, with regard to the fluorine-containing resin (F), for example, the description in WO 2021 / 235541 can be referred to.

[0154] (Colorant (G)) The photosensitive composition of the present embodiment may contain a colorant (G). As one example, by using the colorant (G) to make the resulting pattern (partition wall) black, it is possible to suppress unintended "light seepage" and "color mixing between adjacent pixels" in the light-emitting element. As another example, by using the colorant (G) to make the resulting pattern (partition wall) white, it is possible to increase the reflectance of the pattern (partition wall) and improve the luminance of light emitted from the light-emitting element. Naturally, an appropriate colorant (G) may be selected so as to obtain a pattern that is neither black nor white, depending on various purposes.

[0155] 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.

[0156] 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 and titanium oxide.

[0157] The white pigment is preferably at least one inorganic substance selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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).

[0163] 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.

[0164] (Other Optional Components) The photosensitive composition of this embodiment may 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] (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.

[0166] 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.

[0167] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0168] 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.

[0169] 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.

[0170] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0171] 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.

[0172] Examples of aromatic solvents include xylene and toluene.

[0173] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluorocompounds, and hexafluoroisopropyl alcohol.

[0174] 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.

[0175] 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.

[0176] 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 used in an amount such that the total solids concentration becomes, for example, 5 to 85 mass %, specifically 10 to 60 mass %. By adjusting the amount of solvent, the thickness of the film to be formed can be adjusted. Within the above range, it is easy to obtain a film with a thickness suitable for obtaining partition walls in organic EL elements.

[0177] (Additional Explanation of Storage Stability) As described above, the storage stability of the photosensitive composition of this embodiment is good. This good storage stability can be determined by the mathematical formula: (|η １ -η ０ | / η ０ ) × 100(%). In this formula, η ０ is the viscosity of the photosensitive composition measured using a Brookfield viscometer, and η １ is the viscosity of the photosensitive composition after storage at 40°C for 7 days, measured using a Brookfield viscometer. For details on the viscosity measurement conditions, see the description in the Examples below. The viscosity change rate is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. In other words, by designing the photosensitive composition so that the viscosity change rate falls within the range shown here, the storage stability of the composition can be further improved. The viscosity change rate is ideally 0%.

[0178] <Method and Use of 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 and cured.

[0179] As already explained, the photosensitive composition of this embodiment is preferably used to form partition walls in a light-emitting device. That is, in the series of steps described above, by appropriately designing the "pattern" of the patterned exposure in the exposure step, it is possible to produce partition walls of a desired size and shape (specifically, partition walls having "recesses" for dispensing ink) made of a cured product of the photosensitive composition of this embodiment. Then, it is possible to produce a light-emitting device that includes such partition walls and a light-emitting layer or a wavelength conversion layer disposed in the region (corresponding to the recess) defined by the partition walls. Furthermore, it is possible to produce a display device using the light-emitting device.

[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, and even more preferably 70 to 200°C. By not raising the heating temperature too much, 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] 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.

[0194] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, it should be noted that the present invention is not limited to the Examples.

[0195] First, various measurement methods will be described. [Mole ratio of each structural unit in polymer] １ H-NMR, １９ F-NMR or １３ The weight average molecular weight Mw and molecular weight dispersity (ratio of number average molecular weight Mn to weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, Model HLC-8320GPC) with one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) connected in series, using polystyrene as a standard substance and tetrahydrofuran (THF) as a developing solvent. A refractive index difference detector was used as the detector.

[0196] <Preparation (Synthesis or Preparation) of Raw Materials> [Synthesis of Fluorine-Containing Resin 1] Into a 300 mL glass flask equipped with a stirrer, 2.9 parts by mass of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd.; hereinafter referred to as BTFBE), 2.9 parts by mass of 4-acetoxystyrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St), 12.5 parts by mass of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 6.0 parts by mass of glycerin monomethacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as Gly-MA), and 125 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed at room temperature (about 20°C). Thereafter, 2.3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was further added to the flask, and the mixture was degassed with stirring. Thereafter, the atmosphere in the flask was purged with nitrogen gas, and the internal temperature was raised to 79°C, followed by reaction overnight. In this manner, a precursor solution of fluororesin 1 was obtained.

[0197] The structure of the precursor of fluororesin 1 is as shown below. The composition ratio of the structural units of the precursor of fluororesin 1, in molar ratio, was (structural units derived from BTFBE):(structural units derived from p-AcO-St):(structural units derived from MA-C6F):(structural units derived from Gly-MA)=15:18:29:38.

[0198]

[0199] After completion of the reaction, the atmosphere in the flask was replaced with dry air, and the reaction solution was cooled to an internal temperature of 60°C. After cooling, 0.01 parts by mass of dibutylhydroxytoluene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 11.4 parts by mass of 2-isocyanatoethyl acrylate (a product of Showa Denko K.K., product name: Karenz AOI) were added to the flask and stirred for 4 hours. The stirred solution was then cooled to room temperature (20°C). In this way, a solution of fluororesin 1 was obtained. Based on the results of GPC measurement, the Mw of fluororesin 1 was 13,300, and the Mw / Mn was 1.7.

[0200] [Synthesis of Fluorine-Containing Resin 2] Into a 300 mL glass flask equipped with a stirrer, at room temperature (approximately 20°C), 9.5 g (0.05 mol) of BTFBE, 13.0 g (0.10 mol) of hydroxyethyl methacrylate (hereinafter referred to as HEMA), 43.2 g (0.1 mol) of MA-C6F, 8.6 g (0.10 mol) of methacrylic acid (Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as MAA), 7.8 g (0.75 mol) of styrene (Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as St), and 82 g of MEK (methyl ethyl ketone) were placed. Thereafter, 1.6 g (0.005 mol) of AIBN was further placed in the flask and degassed while stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, the internal temperature was raised to 75°C, and the mixture was allowed to react for 6 hours. In this manner, a precursor solution of fluorine-containing resin 2 was obtained.

[0201] The structure of the precursor of fluororesin 2 is as shown below. The composition ratio of the structural units of the precursor of fluororesin 2, in molar ratio, was structural units derived from BTFBE:structural units derived from HEMA:structural units derived from MA-C6F:structural units derived from MAA:structural units derived from St=15:25:30:10:20.

[0202]

[0203] After the reaction was completed, the atmosphere in the flask was replaced with dry air, and the reaction solution was then cooled to an internal temperature of 60°C. After the temperature was lowered, 0.01 parts by mass of dibutylhydroxytoluene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 12.1 parts by mass of 2-isocyanatoethyl acrylate (a product of Showa Denko K.K., product name: Karenz AOI) were added to the flask and stirred for 4 hours. The stirred solution was then cooled to room temperature (20°C). In this way, a solution of fluororesin 2 was obtained. Based on the results of GPC measurement, Mw=7,200, Mw / Mn=1.3

[0204] [Preparation of Black Pigment Dispersion 1] The pigment, dispersant, alkali-soluble resin, and solvent shown in the table below were mixed in the mass ratios shown in the table below to prepare a mixture. This mixture was dispersed in a bead mill at 25°C for 12 hours using 0.5 mmφ zirconia beads. After the dispersion process was completed, the beads were removed by filtration. In this way, Black Pigment Dispersion 1 was prepared.

[0205]

[0206] [Preparation of Blue Pigment Dispersion] The pigment, dispersant, alkali-soluble resin, and solvent shown in the table below were mixed in the mass ratio shown in the table below to prepare a mixture. This mixture was dispersed in a bead mill at 25°C for 12 hours using 0.5 mmφ zirconia beads. After dispersion was completed, the beads were removed by filtration. In this way, a blue pigment dispersion was prepared.

[0207]

[0208] [Synthesis of Disulfide Compound Solution 1] In a 50 mL glass flask equipped with a stirrer, 1 part by mass of pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., hereinafter referred to as Karenz-MTPE1) and 20 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed at room temperature (approximately 20°C) to prepare a mixture. While stirring the mixture in the flask, oxygen gas was blown into the mixture, and the mixture was allowed to react at room temperature for 1 hour. After completion of the reaction, the PGMEA was removed to obtain Disulfide Compound Solution 1.

[0209] GPC measurement was performed under the same conditions as for measuring the molecular weight of the polymer. The molecular weights and abundance ratios of the components (product and unreacted material) contained in the solution after the reaction were calculated from the peak areas in the chart. As a result, it was confirmed that 12% of the total amount of thiol groups before the reaction had been converted to disulfides.

[0210] [Synthesis of Disulfide Compound Solution 2] A 50 mL glass flask equipped with a stirrer was charged with 1 part by mass of dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals, hereinafter referred to as DPMP) and 20 parts by mass of propylene glycol monomethyl ether acetate at room temperature (approximately 20°C) to prepare a mixture. While stirring the mixture in the flask, oxygen gas was blown into the mixture, and the mixture was allowed to react at room temperature for 30 minutes. After completion of the reaction, the PGMEA was removed to obtain Disulfide Compound Solution 2.

[0211] GPC measurement was performed under the same conditions as for measuring the molecular weight of the polymer. The molecular weights and abundance ratios of the components (product and unreacted material) contained in the solution after the reaction were calculated from the areas of the peaks in the chart. As a result, it was confirmed that 15% of the total amount of thiol groups before the reaction had been converted to disulfides.

[0212] <Preparation of Photosensitive Composition> First, the components used in the examples and comparative examples will be shown.

[0213] [Compounds Having an Ethylenic Carbon-Carbon Double Bond] Ethylenically unsaturated compound 1: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. Ethylenically unsaturated compound 2: "TMMT" (pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0214] [Thiol-based compounds] Thiol-based compound 1: "Karenz-MTPE1" manufactured by Showa Denko K.K. Thiol-based compound 2: "DPMP" manufactured by SC Organic Chemical Industry Co., Ltd.

[0215] [Photoradical initiator] Photoradical initiator 1: "OXE-01" manufactured by BASF Photoradical initiator 2: "TR-PBG-305" manufactured by Tronly

[0216] [Disulfide Compounds] Disulfide Compound 1: Disulfide Compound Solution 1 synthesized as described above. Disulfide Compound 2: Disulfide Compound Solution 2 synthesized as described above. Disulfide Compound 3: Di-tert-butyl disulfide

[0217] [Alkali-soluble resins] Alkali-soluble resin 1: "ZAR-2050H" manufactured by Nippon Kayaku Co., Ltd. (special BIS-A type epoxy acrylate, containing a structural unit represented by the general formula (1) shown above, containing no fluorine atoms). Alkali-soluble resin 2: "ZCR-1569H" manufactured by Nippon Kayaku Co., Ltd. (biphenyl type epoxy acrylate). Alkali-soluble resin 3: "CCR-1171H" manufactured by Nippon Kayaku Co., Ltd. (cresol novolac type epoxy acrylate). Alkali-soluble resin 4: "TR-B20101" manufactured by Tronly (a cardo resin having the following structure, where parentheses indicate a repeating unit).

[0218]

[0219] [Fluororesin] Fluororesin 1: Fluororesin 1 synthesized as described above. Fluororesin 2: Fluororesin 2 synthesized as described above. Fluororesin 3: Surface modifier "Megafac RS-72A" (fluorine-based, polyether structure) manufactured by DIC Corporation.

[0220] [Colorants (Colored Pigment Dispersions)] Black pigment dispersion 1: Black pigment dispersion 1 prepared as described above Black pigment dispersion 2: "NX-593" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (dispersion of carbon black pigment, pigment content: 16% by mass) White pigment dispersion ("NX-501" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (titanium oxide pigment, rutile structure, pigment content: 73% by mass, particle diameter: D50 is 270 nm) Blue pigment dispersion: Blue pigment dispersion prepared as described above

[0221] [Additives] Additive 1: Adhesion improver "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd.

[0222] Each of the components shown in the table below was mixed uniformly with PGMEA as a solvent and stirred to prepare a photosensitive composition. The amount of PGMEA was adjusted to give a non-volatile component concentration of 10% by mass or 50% by mass (two types of photosensitive compositions with different non-volatile component concentrations were prepared).

[0223] <Evaluation> [Formation of Barriers for Evaluation] Barriers (patterns) were formed on a substrate using the following procedure. (1) A 10 cm square ITO substrate was washed with ultrapure water and then with acetone. Then, the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Sources Co., Ltd., Model No. PL17-110). (2) After the UV ozone treatment, a photosensitive composition was applied to the substrate using a spin coater at a rotation speed of 300 rpm. The substrate was then heated on a hot plate at 80°C for 150 seconds. A resin film was thus obtained. (3) Using a mask aligner (manufactured by SUSS MicroTec Co., Ltd.), the resulting resin film was irradiated with i-line light (wavelength 365 nm) through a mask with a line:space ratio of 10 μm:10 μm. (4) Spray development was performed for 40 seconds using a 0.04% by mass potassium hydroxide aqueous solution. After development, the substrate was rinsed with pure water for 10 seconds. The remaining developer and / or rinse solution was then washed away with N ２ The coating was removed by blowing. (5) The substrate was heated on a hot plate at 200° C. for 60 minutes.

[0224] [Evaluation of Sensitivity and Resolution] The exposure dose in (3) of [Formation of barrier ribs for evaluation] above was changed to determine the exposure dose that allows a pattern with a line:space=10 μm:10 μm to be formed on a substrate using a mask pattern with a line:space=10 μm:10 μm, that is, the optimal exposure dose E at which a pattern with the same line width as the mask pattern is resolved. ｏｐ (mJ / cm ２ ) was obtained. ｏｐ was used as an index of sensitivity.

[0225] In addition, the optimum exposure amount E ｏｐThe barrier rib pattern obtained in step 1 was observed under a microscope, and the resolution was evaluated according to the following criteria: - The mask portion that shielded the light, i.e., the total area of ​​the openings, was 100% open (no foreign matter was found), there was no residue in the openings in the barrier ribs, and no line edge roughness was observed: Excellent - The mask portion that shielded the light, i.e., the total area of ​​the openings, was 99 to 90% open (1 to 10% of the openings were filled with foreign matter), and / or line edge roughness was observed: Good - The mask portion that shielded the light, i.e., the total area of ​​the openings, was only 0 to 89% open, and / or line edge roughness was noticeable: Unacceptable

[0226] [Storage Stability: Viscosity Change] The viscosity of the photosensitive composition immediately after preparation was measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd., model DV2T) at a sample temperature of 25°C and a spindle rotation speed of 15 rpm. The spindle used was a Spindle ULA (manufactured by AMETEC). The measurement was performed six times, and the average of the six values ​​obtained was taken as the viscosity (before storage) η ０ Thereafter, the viscosity of the photosensitive composition after storage at 40° C. for 7 days was measured six times in the same manner, and the average value was calculated. The average value of the six obtained values ​​was defined as the viscosity (after storage) η １ Then, the formula: (|η １ -η ０ | / η ０ ) × 100 (%), the viscosity change rate before and after storage was calculated. The evaluation criteria were as follows: Viscosity change rate of 5% or less: Excellent Viscosity change rate of more than 5% but not more than 10%: Good Viscosity change rate of more than 10% but not more than 15%: Acceptable Viscosity change rate of more than 15% or solidification that made measurement impossible: Unacceptable

[0227] [Storage stability: resolution] Using a photosensitive composition that had been left to stand at 40°C for 7 days and aged, partition walls (patterns) were formed in the same manner as in [Formation of partition walls for evaluation]. The partition walls thus obtained were compared with partition walls formed using the photosensitive composition before aging. Evaluation was then performed according to the following criteria. Excellent: 100% of the masked area that shielded the light, i.e., the total area of ​​the openings, was open (no foreign matter was observed). Good: 99-90% of the masked area that shielded the light, i.e., the total area of ​​the openings was open (1-10% of the openings were filled with foreign matter). Fair: 89-80% of the masked area that shielded the light, i.e., the total area of ​​the openings was open (11-20% of the openings were filled with foreign matter). Poor: Only 79% or less of the masked area that shielded the light, i.e., the total area of ​​the openings, was open.

[0228] The following table summarizes information about the components of the photosensitive composition and the evaluation results. In the table, the ratio of the disulfide compound is listed in ppm based on the total nonvolatile components in the composition, and the ratios of the other components are listed by mass ratio. In the table, even for components used in the preparation of the composition in the form of a solution or dispersion, the ratio is listed in terms of the amount of nonvolatile components.

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237] As shown in the table above, the storage stability of the photosensitive compositions of the Examples containing a disulfide compound was good. Furthermore, performance other than storage stability, such as sensitivity and resolution, was also good. From this, it can be seen that the photosensitive compositions containing a disulfide compound exhibit good storage stability and also have good other performance, such as sensitivity. In contrast, the storage stability of the photosensitive compositions of the Comparative Examples not containing a disulfide compound was poorer than that of the Examples.

[0238] This application claims priority based on Japanese Patent Application No. 2023-111634, filed on July 6, 2023, 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) a disulfide compound.

2. The photosensitive composition according to claim 1, wherein the ratio of said disulfide compound (D) in the total non-volatile components is 1 to 30,000 ppm.

3. The photosensitive composition according to claim 1 or 2, wherein the amount of said disulfide compound (D) is 0.01 to 40 parts by mass per 100 parts by mass of said thiol compound (B).

4. The photosensitive composition according to claim 1 or 2, wherein the disulfide compound (D) contains a polymer of the thiol compound (B).

5. The photosensitive composition according to claim 1 or 2, wherein the amount of said thiol compound (B) in the total non-volatile components is 0.1 to 10% by mass.

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

7. The photosensitive composition according to claim 1 or 2, further comprising a fluorine-containing resin (F).

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

9. The photosensitive composition according to claim 1 or 2, wherein the viscosity of the photosensitive composition measured using a B-type viscometer is η ０ The viscosity of the photosensitive composition measured using a B-type viscometer after storing the photosensitive composition at 40° C. for 7 days is defined as η １ Then, (|η １ -η ０ | / η ０ ) × 100(%) is 15% or less.

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

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

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

13. A partition wall according to claim 12, which is for a light emitting element.

14. A light-emitting element comprising the partition wall according to claim 12, and a light-emitting layer or a wavelength conversion layer disposed in an area defined by the partition wall.

15. A display device comprising the light-emitting element according to claim 14.