Photosensitive composition, method for manufacturing a resin-cured film, partition wall, light-emitting element, and display device.

Abstract

To provide a photosensitive composition that cures sufficiently at low temperatures and is preferably used for forming partitions in light-emitting elements. [Solution] A photosensitive composition comprising a compound (A) having an ethylenically active carbon-carbon double bond, one or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors, and a photoradical initiator (C). The ratio of thiol compounds (B) in the total solid content of this photosensitive composition is 10% by mass or more. Furthermore, this photosensitive composition does not contain ultraviolet absorbers, or if it does, it is less than 3% by mass of the total solid content.

Description

Technical Field

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

Background Art

[0002] When manufacturing a light emitting element in a display device such as an organic EL display, a micro LED display, or a quantum dot display, as a method for forming an organic layer having functions such as light emission, ink is dropped into the recesses of a pattern having irregularities formed on a substrate by, for example, an inkjet method, and then the ink is dried and / or solidified. Here, the "pattern having irregularities" may be referred to as a "partition wall" (bank). The partition wall serves as a barrier to prevent the inks from mixing when ink is dropped into the recesses of the pattern. The partition wall preferably has a property of appropriately "repelling" the ink. This is to prevent the ink dropped into a certain recess from "creeping" along the side surface of the partition wall and entering an adjacent recess.

[0003] The partition wall can be formed, for example, by a photolithography method using a photosensitive composition. Therefore, the development of a photosensitive composition for forming a partition wall has been underway.

[0004] As an example, Patent Document 1 describes a photosensitive resin composition for forming a partition wall including a colorant containing a white pigment, a UV absorber, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. In this composition, the value of {(weight% of UV absorber) × (absorbance of UV absorber)} / {(weight% of photopolymerization initiator) × (absorbance of photopolymerization initiator)} is 0.3 to 1.5.

[0005] As another example, Patent Document 2 describes a negative-type photosensitive resin composition containing an alkali-soluble resin or 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. Patent Document 2 also describes forming a partition using this composition. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-132185 [Patent Document 2] International Publication No. 2014 / 084279 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Heating is typically performed during the manufacturing of light-emitting elements, for example, when forming the partitions described above. Specifically, a textured pattern formed using a photosensitive composition is heated and cured to form the partitions. From the viewpoint of suppressing alteration and degradation of dyes and other materials in the light-emitting element, it is preferable to perform the heating for curing at the lowest possible temperature.

[0008] However, according to the inventors' findings, conventional compositions used to form partitions did not harden sufficiently at low temperatures. In other words, conventionally, it was not possible to form partitions that hardened sufficiently at low temperatures.

[0009] This invention has been made in view of these circumstances. One object of this invention is to provide a photosensitive composition that cures sufficiently at low temperatures and is preferably used for forming partitions in light-emitting elements. [Means for solving the problem]

[0010] The inventors have completed the invention described below and solved the above problems. The present invention is as follows:

[0011] 1. Compound (A) having an ethylenically active carbon-carbon double bond, One or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors, Photoradical initiator (C), A photosensitive composition comprising, The proportion of the thiol compound (B) in the total solid content of the photosensitive composition is 10% by mass or more. A photosensitive composition that does not contain ultraviolet absorbers, or if it does, contains less than 3% by mass of the total solids. 2. The photosensitive composition described in 1. The number of moles of the ethylenic carbon-carbon double bond in compound (A) is M. C=C year, The number of moles of mercapto groups in the thiol is M SH1 M is the number of moles of mercapto groups that can be generated from the thiol precursor. SH2 In that case, R=(M SH1 +M SH2 ) / M C=C A photosensitive composition having a value of 0.30 to 8.50. 3. A photosensitive composition as described in 1. or 2., A photosensitive composition in which the aforementioned R is 0.50 to 2.50. 4. A photosensitive composition according to any one of 1. to 3., Furthermore, a photosensitive composition containing an alkali-soluble resin (D). 5. A photosensitive composition according to any one of 1. to 4., Furthermore, a photosensitive composition containing a fluororesin (E). 6. A photosensitive composition according to any one of 1. to 5., Furthermore, a photosensitive composition containing a coloring agent (F). 7. A photosensitive composition according to any one of 1. to 6., A photosensitive composition used to form partitions in light-emitting elements. 8. A film-forming step involves applying a photosensitive composition described in any one of 1. to 7. onto a substrate to form a film, An exposure step of pattern exposure of the aforementioned film, The developing process involves developing the film after exposure, A heating process in which the film after development is heated and hardened, A method for producing a resin-cured film having the following characteristics. 9. A method for producing a resin cured film as described in 8. A method for manufacturing a resin-cured film, wherein in the heating step, the developed film is heated to 50-150°C. 10. A method for producing a resin cured film as described in 8. or 9., A method for manufacturing a resin-cured film, wherein in the heating step, the developed film is heated to 50-100°C. 11. A method for producing a resin cured film as described in any one of 8. to 10., A method for producing a resin-cured film, wherein the film-forming step involves heating the coated photosensitive composition at 50 to 150°C. 12. A partition wall composed of a cured product of any one of the photosensitive compositions described in 1. to 7. 13. The partition described in 12. A partition wall for light-emitting elements. 14. A light-emitting element comprising a partition wall as described in 12. or 13., and a light-emitting layer or wavelength conversion layer disposed in the region partitioned by the partition wall. 15. A display device comprising the light-emitting element described in 14. [Effects of the Invention]

[0012] The present invention provides a photosensitive composition that hardens sufficiently at low temperatures and is preferably used for forming partitions in light-emitting elements. [Modes for carrying out the invention]

[0013] Embodiments of the present invention will be described in detail below. In this specification, the notation "X~Y" in descriptions of numerical ranges means "X or greater and Y or less" unless otherwise specified. For example, "1~5 mass%" means "1 mass% or greater and 5 mass% or less". In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0014] <Photosensitive composition> The photosensitive composition of this embodiment comprises a compound (A) having an ethylenically active carbon-carbon double bond, one or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors, and a photoradical initiator (C). The proportion of thiol compound (B) in the total solid content of the photosensitive composition of this embodiment is 10% by mass or more. The photosensitive composition of this embodiment does not contain ultraviolet absorbers, or if it does, it contains less than 3% by mass of the total solids.

[0015] According to the inventors' findings, the photosensitive composition of this embodiment is thought to harden by the "thiol-ene reaction," which is known in the field of organic chemistry. Specifically, a radical generated from the photoradical initiator (C) reacts with the ethylenic carbon-carbon double bond in compound (A) and the mercapto group in the thiol compound (B) to form a covalent bond. Since the thiol-ene reaction proceeds in a chain reaction, it is possible for one generated radical to form two or more covalent bonds.

[0016] In the photosensitive composition of this embodiment, by setting the ratio of the thiol compound (B) in the total solid content to 10% by mass or more to increase the amount of mercapto groups in the system (increase the density of mercapto groups), it is considered that the thiol-ene reaction proceeds efficiently. As a result, sufficient curing is considered to proceed even at a relatively low temperature.

[0017] From the viewpoint of more efficient progress of the thiol-ene reaction and further improvement of curability at low temperatures thereby, it is preferable to optimize the ratio of the amount of ethylenic carbon-carbon double bonds in the compound (A) and the amount of mercapto groups in the thiol compound (B). Specifically, · Let the number of moles of ethylenic carbon-carbon double bonds in the compound (A) be M C=C , · Let the number of moles of mercapto groups in the thiol as the thiol compound (B) be M SH1 , and the number of moles of mercapto groups that can be generated from the thiol precursor as the thiol compound (B) be M SH2 When, R = (M SH1 + M SH2 ) / M C=C It is preferable to appropriately select and adjust the chemical structure and usage amount of the compound (A), and the chemical structure and usage amount of the thiol compound (B) so that the value of is preferably 0.30 to 8.50, more preferably 0.40 to 5.00, preferably 0.50 to 2.50, still more preferably 0.55 to 2.50, and particularly preferably 0.65 to 2.00.

[0018] Incidentally, there are conventional photosensitive compositions that use compounds having ethylenic carbon-carbon double bonds and thiols. However, thiols are sometimes used as chain transfer agents in the radical polymerization of carbon-carbon double bonds. When thiols are used as chain transfer agents, the amount of thiol used is usually considerably less than the amount of thiol compound (B) in the photosensitive composition of this embodiment (note that in the case of a thiol-ene reaction, the number of moles of carbon-carbon double bonds and the number of moles of mercapto groups should basically be "1:1"). In other words, it is presumed that the main curing mechanism differs between the photosensitive composition of this embodiment, which uses a relatively large amount of thiol compound (B), and conventional photosensitive compositions that use a small amount of thiol.

[0019] Furthermore, the photosensitive composition of this embodiment does not contain an ultraviolet absorber, or if it does, it contains less than 3% by mass of the total solids. As a result, the light necessary for activating the photoradical initiator (C) is not "wasted" by the ultraviolet absorber, which is thought to increase the amount of radicals generated by light irradiation. The increase in the amount of radicals generated is thought to contribute to improved low-temperature curability. In addition, the increase in the amount of radicals generated may also lead to increased sensitivity. The amount of ultraviolet absorber in the photosensitive composition of this embodiment is preferably 0 to 2.5% by mass, more preferably 0 to 2% by mass, particularly preferably 0 to 1% by mass, and most preferably 0% by mass, based on the total solid content. The embodiment in which the ultraviolet absorber is 0% by mass refers to an embodiment in which no ultraviolet absorber is contained at all.

[0020] Furthermore, similar to the point that the photosensitive composition of this embodiment "does not contain ultraviolet absorbers, or contains only small amounts of them," the value of the formula {(weight %) of ultraviolet absorber × (absorbance of ultraviolet absorber)} / {(weight %) of photopolymerization initiator × (absorbance of photopolymerization initiator)} described in Patent Document 1 may be considered. In this embodiment, the value of this formula is preferably 0 to 0.2, more preferably 0 to 0.1. In the above formula, "weight %" can be the solid content concentration (mass %) of the relevant component in the photosensitive composition. Furthermore, "absorbance" can be the absorbance measured using light with a wavelength of 365 nm, and specifically, it can be measured according to the method described in paragraph 0135 of Patent Document 1, etc.

[0021] Incidentally, the ultraviolet absorbers in this embodiment are specifically any of the following: benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers (e.g., BASF's Tinuvin® series), cyanoacrylate-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. These ultraviolet absorbers are also mentioned in paragraphs 0049 to 0057 of Patent Document 1. It is preferable that the photosensitive composition of this embodiment does not contain these ultraviolet absorbers, or contains only a small amount.

[0022] Examples of benzotriazole-based UV absorbers include octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, 2-ethylhexyl 3-(3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl)propionate, [3-[3-(2H-benzotriazole-2-yl)-5-(1,1-methylethyl)-4-hydroxyphenyl]-1-oxopropyl]-w-[3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl), (3-(3-(2H-benzotriazole-2-yl)-5-( Examples include 1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-hydroxypoly(oxo-1,2-ethanediyl), 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-ditert-pentylphenol, 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxybenzenepropionate octyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. Commercially available products include Chiba's CYASORB UV-2337 and CYASORB UV-5411, BASF's TINUVIN 99-2, TINUVIN 171, TINUVIN 213, TINUVIN 326, TINUVIN 360, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, and TINUVIN 1130, and Songwon Industrial's SONGSORB 1000, SONGSORB 2340, SONGSORB 3200, SONGSORB 3260, SONGSORB 3270, and SONGSORB 3280.

[0023] Examples of triazine-based UV absorbers include 2-(4,6-dimethyl-1,3,5-triazine-2-yl)-5-((hexyl)oxy)-phenol, 2-(4-(2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(4-(2-hydroxy-3-didecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Examples include 2-(2-hydroxy-4-(3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy)phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]bis(5-butoxyphenol), and 6-methylheptyl 2-{4-[4,6-di(4-biphenylyl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxy}propanoate. Commercially available products include CYTEC's CYASORB UV-1164, and BASF's TINUVIN 1577, TINUVIN P, TINUVIN 234, TINUVIN 328, TINUVIN 329, TINUVIN 400, TINUVIN 479, and TINUVIN 571.

[0024] Examples of hindered amine-based UV absorbers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], which contain a 2,2,4,6-tetramethylpiperazine structure.

[0025] Examples of cyanoacrylate-based UV absorbers include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, and alkynyl-2-cyanoacrylate.

[0026] Examples of benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone (SeeSorb 106, Cipro Chemical Co., Ltd.), and 2,2'-dihydroxy-4-methoxybenzophenone (KEMISORB 111, Chemipro Chemical Co., Ltd.).

[0027] Furthermore, in Patent Document 1, the use of an ultraviolet absorber is preferred, particularly because a colorant containing a white pigment is used. However, since the photosensitive composition of this embodiment does not require a white pigment as an essential component, sufficient performance can be obtained without using an ultraviolet absorber. Of course, even if the photosensitive composition of this embodiment contains a white pigment, it can either not contain an ultraviolet absorber at all, or contain only a small amount.

[0028] The following describes the components that the photosensitive composition of this embodiment may contain, as well as other specific aspects of the photosensitive composition of this embodiment.

[0029] [Compounds containing ethylenic carbon-carbon double bonds (A)] Compound (A) can be any compound having an ethylenically active carbon-carbon double bond without particular limitation. "Ethylenelylic carbon-carbon double bond" means a carbon-carbon double bond that can react by the action of a radical, and in this embodiment in particular, a carbon-carbon double bond that can react with the thiol compound (B). Conjugated-stabilized double bonds, such as the double bond of a benzene ring, do not qualify as "ethylenically active carbon-carbon double bonds". From the viewpoint of improving reactivity, it is preferable that compound (A) has an ethylenic carbon-carbon double bond at its terminus.

[0030] Compound (A) may be monofunctional or polyfunctional. That is, compound (A) may have only one ethylenically active carbon-carbon double bond in one molecule, or it may have two or more (specifically 2 to 8, more specifically 2 to 6) ethylenically active carbon-carbon double bonds in one molecule. From the viewpoint of further improving low-temperature curability and enhancing the physical properties of the cured film, compound (A) is preferably polyfunctional.

[0031] Preferably, compound (A) is a (meth)acrylate compound, that is, a compound having a (meth)acryloyl group as a structure containing an ethylenic carbon-carbon double bond. More preferably, compound (A) is a (meth)acrylate compound.

[0032] Specific examples of compound (A) include the following. Of course, compound (A) is not limited to these.

[0033] 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, and dipentaerythritol hexa(meth)acrylate; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; and urethane(meth)acrylates obtained by the reaction of polyisocinate with hydroxyl group-containing(meth)acrylates such as hydroxyethyl(meth)acrylate.

[0034] The photosensitive composition of this embodiment may contain only one compound (A), or it may contain two or more compounds (A). The content of compound (A) is usually 5 to 60% by mass, preferably 10 to 50% by mass, and more preferably 10 to 40% by mass, of the total solid content of the photosensitive composition. Incidentally, as mentioned above, the content of compound (A) is M, which is the number of moles of mercapto groups in the thiol as thiol compound (B). SH1 M is the number of moles of mercapto groups that can be generated from a thiol precursor as a thiol compound (B). SH2 It is preferable to make adjustments taking this into consideration. The content ratio of double bonds (C=C) in compound (A) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and more preferably 10 to 30% by mass.

[0035] [Thiol compounds (B)] The photosensitive composition of this embodiment contains one or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors.

[0036] The thiol compound (B) may be monofunctional or polyfunctional. That is, the thiol compound (B) may have only one mercapto group (or potential mercapto group) in one molecule, or it may have two or more (specifically 2 to 8) mercapto groups (or potential mercapto groups) in one molecule. From the viewpoint of further improving low-temperature curability and enhancing the physical properties of the cured film, it is preferable that the thiol compound (B) is polyfunctional.

[0037] Specifically, the thiol in thiol compounds (B) can be represented by the following general formula (b).

[0038] [ka]

[0039] In general formula (b), R is a hydrogen atom, an alkyl group, or a cycloalkyl group. X is -CO- or -CH2-, L is an n-valent linking group, n is an integer greater than or equal to 2, preferably between 2 and 8, more preferably between 2 and 6. Multiple Rs may be identical or different from each other. Similarly, multiple Xs may be identical or different from each other. However, from the viewpoint of ease of composition, it is preferable that multiple Rs are identical, and it is preferable that multiple Xs are identical.

[0040] The alkyl group R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 1 to 10. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and 2-ethylhexyl group. Among these, methyl group, ethyl group, propyl group, or isopropyl group are preferred, and methyl group or ethyl group are more preferred.

[0041] Examples of the n-valent linking group L include linear or branched alkylene chains (e.g., 2-6 carbon atoms), trimethylolpropane residues, and -(CH2) p Examples include trivalent linking groups such as isocyanuric rings having three -(p is 2-6), tetravalent or pentavalent linking groups such as pentaerythritol residues, and hexavalent linking groups such as dipentaerythritol residues.

[0042] Commercially available thiols for thiol compounds (B) include, for example, the "Karenz" series manufactured by Showa Denko K.K. The thiols in this series are secondary thiols. Other examples include the product codes "PEMP," "TMMP," "DPMP," and "TEMPIC" from SC Organic Chemicals Co., Ltd. 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 sufficiently good results even with secondary thiols. Incidentally, secondary thiols may have improved compositional stability because the reaction of the thiol group is suppressed due to steric hindrance.

[0043] In thiol compounds (B), a "thiol precursor" refers to a compound that does not itself possess a mercapto group but produces one in the composition through physical stimulation or chemical action. Examples of thiol precursors include thioesters, dithioesters, thiocarbamates, dithiocarbamates, thiocarbonates, xanthogenicates, and trithiocarbonates. The specific structure of a thiol precursor may be, for example, one in which the -SH portion of the general formula (b) above is esterified or in the form of a salt. Thiol precursors are described, for example, in Japanese Patent Publication No. 2004-517979.

[0044] The photosensitive composition of this embodiment may contain only one thiol compound (B), or it may contain two or more thiol compounds (B). The content of thiol compound (B) is usually 10 to 70% by mass, preferably 15 to 60% by mass, and more preferably 20 to 55% by mass, of the total solid content of the photosensitive composition. Incidentally, as mentioned above, it is preferable to adjust the content of thiol compound (B) while also taking into account the amount of compound (A). The mercapto group content of thiol compound (B) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and more preferably 10 to 30% by mass, relative to the molecular weight of thiol compound (B). Incidentally, if thiol compound (B) is a thiol precursor, this value is calculated based on the chemical structure after the thiol precursor is converted to the thiol compound.

[0045] Incidentally, an indicator that correlates well with the content of thiol compound (B) is the sulfur atom content in the cured film when the photosensitive composition of this embodiment is cured. When the photosensitive composition of this embodiment is used to form a cured film, the sulfur atom content in the cured film is, for example, 2.0 to 20% by mass, preferably 2.5 to 15% by mass, and more preferably 3.0 to 14% by mass. For information on how to measure the sulfur atom content in the cured film, please refer to the examples provided below.

[0046] [Photoradical initiator (C)] The photosensitive composition of this embodiment contains a photoradical initiator (C). There are no particular restrictions on the photoradical initiator (C), as long as it generates radicals when irradiated with light (typically ultraviolet light such as i-rays).

[0047] Examples of photoradical initiators include intramolecular cleavage types, which generate radicals by breaking bonds within the molecule upon absorption by electromagnetic waves or electron beams, and hydrogen abstraction types, which generate radicals by using hydrogen donors such as tertiary amines or ethers in combination. Any of these may be used. Of course, other photoradical initiators can also be used.

[0048] Examples of photoradical initiators include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based compounds.

[0049] Examples of benzophenone-based photoradical initiators include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0050] Examples of acetophenone-based photoradical initiators 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0051] Examples of diketone-based photoradical initiators include 4,4'-dimethoxybenzyl, methyl benzoylmate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylmate are preferred.

[0052] Examples of acylphosphine oxide initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0053] Examples of quinone-based initiators include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0054] Examples of acyloin initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

[0055] Among commercially available photoradical initiators, preferred examples include BASF products such as Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, and Lucilin TPO.

[0056] The photosensitive composition of this embodiment may contain only one photoradical initiator (C), or it may contain two or more photoradical initiators (C). The content of the photoradical initiator (C) may be adjusted as appropriate, taking into consideration sufficient sensitivity and resolution. The content of the photoradical initiator (C) is usually 0.1 to 10% by mass, preferably 0.3 to 8% by mass, and more preferably 0.5 to 5% by mass, of the total solid content of the photosensitive composition.

[0057] [Alkali-soluble resin (D)] The photosensitive composition of this embodiment preferably contains an alkali-soluble resin (D). By using the alkali-soluble resin (D), it tends to be easier to form patterns of a desired shape, especially when forming patterns (septa) using an alkaline developer. Incidentally, in this specification, resins that contain fluorine atoms and are alkali-soluble are generally classified as fluorine-containing resins (E), as described below. In other words, alkali-soluble resins (D) generally do not contain fluorine atoms.

[0058] Examples of alkali-soluble resins (D) include alkali-soluble novolac resins. Alkali-soluble novolac resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst. 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-methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol. These phenols may be used individually or in combination of two or more. 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. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethyl sulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used individually or in combination of two or more types.

[0059] Acid-modified epoxy acrylates can also be used as alkali-soluble resins (D). Examples of commercially available acid-modified epoxy acrylates include those manufactured by Nippon Kayaku Co., Ltd., such as 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.

[0060] Examples of alkali-soluble resins (D) include epoxy resins, such as bisphenol A type epoxy resins. Specifically, examples include bisphenol A type epoxy resins having structural units represented by the following general formula (d).

[0061] [ka]

[0062] In general formula (d), Each of the two R's independently represents a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. Z represents a monovalent organic group or hydrogen atom. However, in at least some of the structural units represented by general formula (d) in the alkali-soluble resin (D), Z is a monovalent organic group having a carboxyl group.

[0063] Bisphenol A type epoxy resin having a structural unit represented by general formula (d) is available, for example, from Nippon Kayaku Co., Ltd.

[0064] The weight-average molecular weight of the alkali-soluble resin (D) is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive composition.

[0065] When using alkali-soluble resin (D), you may use only one alkali-soluble resin (D), or you may use two or more alkali-soluble resins (D). When alkali-soluble resin (D) is used, its amount is usually 10 to 70% by mass, preferably 15 to 60% by mass, and more preferably 20 to 55% by mass, of the total solid content of the photosensitive composition.

[0066] [Fluorine resin (E)] The photosensitive composition of this embodiment preferably contains a fluororesin (E). By forming a pattern (separator) with irregularities using a photosensitive composition containing a fluororesin (E), the resulting pattern (separator) becomes more resistant to repelling ink for forming the organic layer. This helps to prevent ink dropped into a recess from "crawling" along the side of the recess and entering adjacent recesses. In other words, it is possible to suppress unintended mixing of dyes between pixels.

[0067] The usable fluororesin (E) is not particularly limited. The following describes some fluororesin (E) that can be preferably used. The fluororesin (E) preferably has a structure represented by the following general formula (1), and more preferably has a structure represented by the following general formula (2).

[0068] [ka]

[0069] In general formula (1), Each of the two Rf elements independently represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms, or a fluorine atom. R 2 This represents a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.

[0070] [ka]

[0071] In general formula (2), Each of the two Rf elements independently represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms, or a fluorine atom. R 1 This represents a hydrogen atom, a fluorine atom, or a methyl group. R 2This represents a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms.

[0072] In general formula (2), R 1 A hydrogen atom or a methyl group is preferred. Also, R 2 Examples of suitable groups include hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, 1-methylpropyl groups, 2-methylpropyl groups, tert-butyl groups, n-pentyl groups, isopentyl groups, 1,1-dimethylpropyl groups, 1-methylbutyl groups, 1,1-dimethylbutyl groups, n-hexyl groups, cyclopentyl groups, and cyclohexyl groups. Hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, and isopropyl groups are preferred, while hydrogen atoms and methyl groups are more preferred.

[0073] In general formula (1) or general formula (2), Rf 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.

[0074] A preferred specific structure of the above structural unit is the structure described in paragraphs 0060-0061 of International Publication No. 2021 / 235541.

[0075] The content of the structural unit represented by general formula (2) in the fluororesin (E) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass, taking into consideration solubility in solvents and resistance to various treatments in the manufacture of light-emitting elements.

[0076] The fluororesin (E) may contain a structure represented by the following general formula (3).

[0077] [ka]

[0078] In general formula (3), R 3 , R 4 Each of these independently represents either a hydrogen atom or a methyl group.

[0079] In general formula (3), W 1 represents a divalent linking group. Preferably, it represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. In particular, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH- are preferred. 1 However, the -OC(=O)-NH- structure is preferable because it provides superior liquid repellency against ink after UV ozone treatment or oxygen plasma treatment in the manufacturing of light-emitting elements.

[0080] In general formula (3), A 1 represents a 2- to 4-valent 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 a hydroxyl group or -OC(=O)-CH3.

[0081] Divalent linking group A 1When it refers to a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0082] Divalent linking group A 1 When this refers to a branched alkylene group having 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene groups.

[0083] Divalent linking group A 1 When it is a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0084] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include hydroxyethylene, 1-hydroxy-n-propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene, 2-hydroxy-n-butylene, hydroxy-sec-butylene (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene (-C(CH2OH)(CH3)CH2-).

[0085] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, an example of such a substituted alkylene group is one in which the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is replaced with -OC(=O)-CH3.

[0086] In particular, divalent linking group A 1 The linking group A is preferably a methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 2-hydroxy-n-butylene group, or hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), more preferably an ethylene group, propylene group, 2-hydroxy-n-propylene group, or hydroxy-isopropylene group (-CH(CH2OH)CH2-), and particularly preferably an ethylene group or a 2-hydroxy-n-propylene group. 1 Examples include -C(CH2-)2CH3, which has a tetravalent linking group A 1 Examples include C(CH2-)4.

[0087] In general formula (3), Y 1 represents a divalent linking group, which is preferably -O- or -NH-, and more preferably -O-.

[0088] In general formula (3), u represents an integer between 1 and 3, and it is particularly preferable that u is 1. In general formula (3), n represents an integer from 1 to 3, and it is particularly preferable that n is 1. The substitution positions of the aromatic ring independently represent the ortho, meta, and para positions, and it is preferable that n be the para position. Multiple Ws exist 1 These may be the same or different from each other. Also, there may be multiple A 1 These can be the same or different from each other. Also, there can be multiple Y's. 1 These may be identical or different from one another. There may be multiple R's. 4 These may be identical or different from one another. However, from the standpoint of ease of synthesis, etc., multiple Ws may exist. 1 It is preferable that they are all the same, and there are multiple A 1 It is preferable that they are all the same, and there are multiple Y 1 It is preferable that they are all the same, and there are multiple R4 It is preferable that they are identical to each other.

[0089] A specific example of a structure represented by general formula (3) that is particularly preferred is the structure described in paragraphs 0081-0084 of International Publication No. 2021 / 235541.

[0090] The content of the structural unit represented by general formula (3) in the fluororesin (E) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass, taking into consideration solubility in solvents and resistance to various treatments in the manufacture of light-emitting elements.

[0091] The fluororesin (E) may contain a structure represented by the following general formula (4).

[0092] [ka]

[0093] In general formula (4), R 5 , R 6 Each of these independently represents either a hydrogen atom or a methyl group.

[0094] In equation (4), W 2 represents a divalent linking group, preferably -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH- are preferred. In particular, W 2 However, when it is -OC(=O)-NH-, it is preferable because it exhibits better liquid repellency against ink after UV ozone treatment or oxygen plasma treatment in the manufacturing of light-emitting elements.

[0095] In general formula (4), A 2represents 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 hydroxyl groups or -OC(=O)-CH3. In general formula (4), A 3 represents a 2- to 4-valent 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 a hydroxyl group or -OC(=O)-CH3.

[0096] Divalent linking group A 2 , A 3 When it refers to a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0097] Divalent linking group A 2 , A 3 These can be any branched alkylene groups having 3 to 10 carbon atoms, such as isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene.

[0098] Divalent linking group A 2 , A 3 When each of these is independently a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0099] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene group (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene group (-C(CH2OH)(CH3)CH2-).

[0100] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, an example of a substituted alkylene group can be found in which the hydroxyl group of the aforementioned hydroxyl group-substituted alkylene group is replaced with -OC(=O)-CH3.

[0101] In particular, divalent linking group A 2 , A 3 These are, independently, 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)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH2OH)CH2-), a 2-hydroxy-n-butylene group, and a hydroxy-sec-butylene group (-CH(CH 2OH)CH2CH2- is preferred, ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-) is more preferred, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH2-), and 2-hydroxyethylene group (-CH2CH(OH)-) are particularly preferred. Examples of trivalent linking groups A3 include -C(CH2-)2CH3, and examples of tetravalent linking groups A3 include C(CH2-)4.

[0102] In general formula (4), Y 2 , Y 3 Each of these independently represents a divalent linking group, which is preferably -O- or -NH-, and more preferably -O-.

[0103] In general formula (4), n represents an integer between 1 and 3. It is particularly preferable that n is 1. Multiple Ys exist 3 These may be identical or different from one another. Also, there may be multiple R's. 6 These may be identical or different from one another. However, from the standpoint of ease of composition, there may be multiple Y 3 It is preferable that they are all the same, and there are multiple R 6 It is preferable that they are identical to each other.

[0104] In general formula (4), r represents either 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0105] A specific example of a structure represented by general formula (4) that is particularly preferred is the structure described in paragraphs 1005-109 of International Publication No. 2021 / 235541.

[0106] The content of the structural unit represented by general formula (4) in the fluororesin (E) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass, taking into consideration solubility in solvents and adhesion of the pattern (partition) to the substrate.

[0107] The fluororesin (E) may contain structural units represented by general formula (5).

[0108] [ka]

[0109] In general formula (5), R 7 represents a hydrogen atom or a methyl group.

[0110] In general formula (5), R 8 The group consists of 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. Any number of hydrogen atoms in these alkyl groups are substituted with fluorine atoms, and the fluorine content in the structural unit is 30% by mass or more.

[0111] R 8 When the group is a linear hydrocarbon group, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or any number of hydrogen atoms of a linear alkyl group having 10 to 14 carbon atoms substituted with fluorine atoms.

[0112] R 8 When is a linear hydrocarbon group, the structural unit represented by general formula (5) is preferably the structural unit represented by general formula (5-1) below.

[0113] [ka]

[0114] In general formula (5-1), R 9 R in general formula (5) 7 It is synonymous with [the above].

[0115] In general formula (5-1), X is a hydrogen atom or a fluorine atom. It is preferable that X is a fluorine atom.

[0116] In general formula (5-1), p is an integer between 1 and 4, and q is an integer between 1 and 14. It is particularly preferable that p is an integer between 1 and 2, and q is an integer between 2 and 8.

[0117] Specific examples of preferred structural units represented by general formula (5) include the structures described in paragraphs 0125-0128 of International Publication No. 2021 / 235541.

[0118] The content of the structural unit represented by general formula (5) in the fluororesin (E) can be appropriately determined by taking into consideration factors such as the ease with which ink is repelled when used as a pattern (partition) and the ease with which it is soluble in solvents when preparing the photosensitive composition. Specifically, the content of the structural unit represented by general formula (5) in the fluororesin (E) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0119] Fluorine-containing resins may include a structure represented by the following general formula (6).

[0120] [ka]

[0121] In general formula (6), R 10 represents a hydrogen atom or a methyl group.

[0122] In general formula (6), B is independently a hydrogen atom, a hydroxyl group, a carboxyl group, and -C(=O)-OR 11 (R 11 R 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, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. 11 (The fluorine content inside is 30% by mass or more) or -OC(=O)-R 12 (R 12 This represents a linear alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms. Also, m represents an integer between 0 and 3.

[0123] A specific example of a structure represented by general formula (6) that is particularly preferred is the structure described in paragraphs 0137-0138 of International Publication No. 2021 / 235541.

[0124] The content of the structural unit represented by general formula (6) in the fluororesin (E) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass, taking into consideration the ability to fully obtain the effects based on the structural unit represented by general formula (6) and solvent solubility.

[0125] In general formula (6), B 1 When is a hydroxyl group or a carboxyl group, the structural unit represented by general formula (6) is soluble in alkaline developing solution. Therefore, if particularly good alkaline developing properties are desired, B is added to the fluororesin (E). 1 It is preferable that the structural unit is represented by general formula (6) when is a hydroxyl group or a carboxyl group.

[0126] The fluororesin (E) may contain a structure represented by the following general formula (7).

[0127] [ka]

[0128] In general formula (7), R 13 represents a hydrogen atom or a methyl group.

[0129] 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 hydroxyl groups or -OC(=O)-CH3.

[0130] Divalent linking group A 4When it refers to a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0131] Divalent linking group A 4 When this refers to a branched alkylene group having 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene groups.

[0132] Divalent linking group A 4 When it is a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0133] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene group (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene group (-C(CH2OH)(CH3)CH2-).

[0134] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, the substituted alkylene group can be said to be the one in which the hydroxyl group of the hydroxyl group-substituted alkylene group described above is replaced with -OC(=O)-CH3.

[0135] In particular, divalent linking group A 4 These are methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)) CH2CH2- is preferred, ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-) is more preferred, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH2-), and 2-hydroxyethylene group (-CH2CH(OH)-) are particularly preferred.

[0136] In general formula (7), Y 4 represents a divalent linking group, preferably -O- or -NH-, and more preferably -O-.

[0137] In general formula (7), r represents either 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0138] In general formula (7), E 1 This represents a hydroxyl group, a carboxyl group, or an oxirane group. E 1 When the group is an oxirane group, examples include ethylene oxide, 1,2-propylene oxide, and 1,3-propylene oxide. Among these, ethylene oxide is preferred.

[0139] In general formula (7), s represents either 0 or 1. When s is 0, (-Y 4 -A 4 -) represents a single bond. When r is 0 and s is 0, E is present in the main chain of the structural unit. 1 This results in a structure where these elements are joined together.

[0140] A specific example of a structure represented by general formula (7) that is particularly preferred is the structure described in paragraph 0156 of International Publication No. 2021 / 235541.

[0141] The weight-average molecular weight of the fluororesin (E), as measured by gel permeation chromatography (GPC) using polystyrene as the 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. By adjusting the molecular weight of the fluororesin (E), it may be possible to increase the strength of the formed pattern (separator) or improve its solubility in solvents, thereby enhancing its coatability.

[0142] The degree of dispersion (Mw / Mn) of the fluororesin (E) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

[0143] The fluororesin (E) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of dispersing each property appropriately rather than locally, a random copolymer is preferred.

[0144] The fluorine content of the fluororesin (E) is preferably 20-50% by mass, and more preferably 25-40% by mass. Having a fluorine content within this range makes the fluororesin (E) easily soluble in solvents. Furthermore, having a fluorine content within this range makes it easier to obtain patterns (barriers) with excellent liquid-repellent properties. The fluorine content of fluororesins (E) can be measured, for example, in accordance with the description in paragraph 0174 of International Publication No. 2021 / 235541.

[0145] When using fluororesin (E), you may use only 1 of fluororesin (E), or you may use 2 or more of fluororesin (E). In order to balance the sufficient liquid repellency of the resulting pattern (septum) with good alkaline developability, the amount of fluororesin (E) used when it is used is usually 0.1 to 10% by mass, preferably 0.1 to 8% by mass, and more preferably 0.5 to 5% by mass, of the total solid content of the photosensitive composition.

[0146] For further information regarding fluoropolymers (E), refer to the description in, for example, International Publication No. 2021 / 235541.

[0147] [Coloring agent (F)] The photosensitive composition of this embodiment may contain a colorant (F). For example, by using a coloring agent (F) to make the resulting pattern (septum) black, it may be possible to suppress unintended "light bleeding" and "color mixing between adjacent pixels" in the light-emitting element. As another example, by using a coloring agent (F) to make the resulting pattern (septum) white, the reflectivity of the pattern (septum) can be increased, and the brightness of the light emitted from the light-emitting element can be improved.

[0148] As the coloring agent (F), a pigment or a dye may be used. Multiple coloring agents may be used in combination as needed. Incidentally, if the resulting pattern (septum) is to be black, a black pigment such as carbon black can be used, or black can be obtained by mixing multiple non-black pigments. If the resulting pattern (septum) is to be gray, gray can be obtained by mixing a black pigment and a white pigment. It is preferable to use organic pigments as the pigments.

[0149] Specific examples of colorants (F) include known colorants such as perylene pigments, lactam pigments, azo pigments, phthalocyanine pigments, carbon pigments such as carbon black, or metal oxide pigments such as iron black or titanium dioxide.

[0150] 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, which makes it easy to improve the light reflectivity of the formed partition wall. Titanium oxide is particularly preferred from the viewpoint of a high refractive index and good dispersibility in the composition.

[0151] Other coloring pigments that can be used include various organic pigments such as yellow, orange, blue, red, green, purple, and brown. Pigment dispersions containing two or more organic pigments may also be used. Optical properties such as solubility and light-shielding properties can be controlled by adjusting the type and ratio of pigments used. In particular, a combination of blue, purple, and orange is preferred from the viewpoint of compatibility and uniformity of optical density.

[0152] Examples of organic orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, CI Pigment Orange 43 is preferred from the viewpoint of dispersibility and light-shielding properties.

[0153] Examples of organic blue pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, and 80. Among these, CI Pigment Blue 60 is preferred from the viewpoint of dispersibility and light-shielding properties.

[0154] Examples of organic purple pigments include CI 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, CI Pigment Violet 23 is preferred from the viewpoint of dispersibility and light-shielding properties.

[0155] When a pigment is used as the coloring agent (F), it is preferable that the pigment be subjected to a dispersion treatment. Dispersion of the pigment can be obtained, for example, by treating the pigment, dispersant, and optionally a solvent using a bead mill. The type of dispersant is not particularly limited, and dispersants available from, for example, Bic Chemie can be used.

[0156] When using colorants (F), you may use only one colorant (F), or you may use two or more colorants (F) in combination. When using a colorant (F), its amount should be adjusted appropriately based on a balance between obtaining sufficient effects from the colorant (F) and the patternability, developability, and strength of the resulting pattern (septum). Specifically, when using a colorant (F), its amount is usually 1 to 60% by mass, preferably 5 to 55% by mass, and more preferably 10 to 50% by mass, of the total solid content of the photosensitive composition. If the colorant (F) is dispersed with a dispersant, the amount of colorant (F) including the dispersant should be within the numerical range shown here.

[0157] [Other optional components] The photosensitive composition of this embodiment may contain any other components besides those listed above. Examples of optional components include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesion improvers, and antioxidants. Commercially available products can be used for these optional components. For example, as an adhesion improver, products from the "KAYAMER" series manufactured by Nippon Kayaku Co., Ltd. can be used.

[0158] [solvent] The photosensitive composition of this embodiment is typically a mixture of the above-mentioned components dissolved or dispersed in a solvent. The solvent typically includes an organic solvent.

[0159] The solvents that can be used are not particularly limited. Specifically, examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorinated solvents. These may be used individually or in mixtures of two or more.

[0160] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0161] 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-hexisanol, 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.

[0162] Examples of polyhydric alcohols and their derivatives 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), and monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0163] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0164] 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.

[0165] Examples of aromatic solvents include xylene and toluene.

[0166] Examples of fluorinated solvents include chlorofluorocarbons (CFCs), alternative CFCs, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0167] In addition, to improve coating properties, high-boiling point weak solvents such as turpentine-based petroleum naphtha solvents or paraffin-based solvents can be used.

[0168] 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, it contains at least one selected from the group consisting of tate 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 is more preferably methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

[0169] When using solvents, you may use only one solvent, or you may use two or more solvents. When using a solvent, it is preferable that the amount of solvent in the photosensitive resin composition be such that the total solids concentration is, for example, 5 to 85% by mass, specifically 10 to 60% by mass. The thickness of the formed film can be adjusted by adjusting the amount of solvent. Within the above range, it is particularly easy to obtain a film thickness suitable for obtaining partitions in organic EL elements.

[0170] <Methods of use and applications of photosensitive compositions> A resin-cured film can be manufactured by using the photosensitive composition of this embodiment and performing a series of steps including, for example, the following film-forming step, exposure step, development step, and heating step. A film-forming process in which the photosensitive composition of this embodiment is applied to a substrate to form a film. Exposure process for pattern exposure of a film The developing process involves developing the film after exposure. Heating process: The film is heated and cured after development.

[0171] As already mentioned, the photosensitive composition of this embodiment is preferably used to form partitions in a light-emitting element. In other words, by appropriately designing the "pattern" of the pattern exposure in the exposure process in the series of steps described above, it is possible to manufacture partitions of a desired size and shape (specifically, partitions having "recesses" for dropping ink) made of cured product of the photosensitive composition of this embodiment. Furthermore, a light-emitting element can be manufactured that comprises such a partition wall and a light-emitting layer or wavelength conversion layer positioned in the region (corresponding to a recess) partitioned by the partition wall. Furthermore, a display device can be manufactured using this light-emitting element.

[0172] The following describes a method for manufacturing a resin-cured film (specifically, a partition wall in a light-emitting element) using the photosensitive composition of this embodiment.

[0173] [Film forming process] In the film-forming process, the photosensitive composition of this embodiment is applied to a substrate to form a film.

[0174] The type of substrate is not particularly limited. The substrate should be selected appropriately depending on the product to be manufactured. Examples of substrate types include silicon wafers, metals, glass, ITO substrates, substrates containing metal oxides, and synthetic resins (polyimide, polycarbonate, polyester). A layer may be formed on at least one side of the substrate. For example, when manufacturing a light-emitting device, a first light-emitting layer may be arranged on at least one side of the substrate. Examples of the first light-emitting layer include a layer formed from organic EL light-emitting material, LED light-emitting material such as mini-LEDs, μ-LEDs, and nano-LEDs, and quantum dot light-emitting material. The first light-emitting layer may be a monochromatic layer or a multi-colored layer, but a monochromatic layer is preferred. Furthermore, it is preferable that the first light-emitting layer is a monochromatic blue light-emitting layer. If the first light-emitting layer is located on at least one side of the substrate, an organic or inorganic film may be provided between the substrate and the first light-emitting layer. For example, this could include an anti-reflective film, a layer under a multilayer resist, or a barrier layer. Furthermore, a drive circuit, electrodes, or a planarization layer may be formed between the substrate and the first light-emitting layer. Alternatively, a wavelength conversion layer may be provided instead of the first light-emitting layer. Just to clarify, a substrate without a first light-emitting layer or other layers formed on its surface may also be used.

[0175] The method for applying the photosensitive resin composition is not particularly limited. Known methods such as spin coating, bar coating, and curtain coating can be used. Inkjet methods may also be applicable. When a photosensitive resin composition containing a solvent is used, it is preferable to dry the solvent by heating after applying the photosensitive resin 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) is typically 0.5 to 20 μm, preferably 1 to 15 μm.

[0176] [Synthesis process] In the exposure process, the film obtained in the film-forming process is pattern-exposed. Specifically, light generated from the light source of the exposure apparatus is irradiated onto the film via a photomask. Here, the light can be ultraviolet, gamma rays, X-rays, etc. Due to the ease of obtaining the light source, ultraviolet light (especially g-rays and i-rays) is mainly used. The exposure dose is not particularly limited, but is typically 1-200 mJ / cm². 2 Preferably 10-100 mJ / cm² 2 That is the case. After exposure and before the development process described later, heat treatment may or may not be applied.

[0177] [Development process] In the development process, the film after exposure is typically developed using a developer. This usually dissolves the unexposed areas within the film, resulting in a pattern (septum).

[0178] An alkaline aqueous solution is preferably used as the developing solution. Specifically, aqueous solutions of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), sodium hydroxide, potassium hydroxide, etc., can be used. As a developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferred, given its good developing properties 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, and more preferably 2 to 3% by mass. Incidentally, in some cases, a developing solution primarily composed of organic solvents can be used.

[0179] Known development methods can be used. Examples include the dip method, paddle method, and spray method. The development time (the time the developer is in contact with the film) is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0180] After the development process, a step may be included to wash the pattern using deionized water or the like, if necessary. The washing time is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0181] [Heating process] In the heating step, the developed film is heated. This allows the remaining ethylenically active carbon-carbon double bonds and mercapto groups within the pattern obtained in the development step to react as much as possible, thereby curing the film. In this embodiment, the film can be cured even if the heating temperature is relatively low. In the heating process, the developed film is heated to, for example, 50-150°C, preferably 50-100°C, more preferably 60-90°C, even more preferably 70-90°C, and particularly preferably 80-90°C. By keeping the heating temperature relatively low, it is easier to suppress the alteration and deterioration of the dyes and other materials in the light-emitting element. Furthermore, the heating time is, for example, 10 minutes to 3 hours, preferably 15 minutes to 1 hour.

[0182] [Optional steps after the heating process] The cured film obtained in the heating process may be subjected to UV ozone treatment or oxygen plasma treatment. This makes it possible to remove organic matter remaining in the recesses of the pattern (cured film) and to reduce uneven wetting of the dropped ink during the ink dropping process described later.

[0183] To obtain a light-emitting element, it is preferable to perform a second light-emitting layer formation step, in which a second light-emitting layer is formed in the recesses of the pattern (cured film), i.e., regions partitioned by partitions, which emit light using light from the first light-emitting layer as excitation light. It is preferable that the second light-emitting layer contains a conventionally known material, such as a quantum dot light-emitting material. The second light-emitting layer can be formed, for example, by dropping ink into the recesses of a pattern (cured film) by an inkjet method as described in the background art section, and then drying and / or solidifying the ink. That is, in some cases, a light-emitting element can be obtained by dropping ink for forming the second light-emitting layer into the recesses of a pattern (cured film) by an inkjet method.

[0184] Alternatively, in order to obtain a light-emitting element that emits RGB light, ink (typically a liquid in which pigments are dispersed) containing red, green, or blue pigments may be dropped into the recesses of a pattern (cured film), that is, the regions partitioned by partition walls, and then the ink may be dried and / or solidified.

[0185] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than those described above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

Examples

[0186] Embodiments of the present invention will be described in detail based on examples and comparative examples. Just to be on the safe side, the present invention is not limited only to the examples.

[0187] [Measurement of the molar ratio of each constitutional unit in the polymer] The molar ratio of each constitutional unit in the polymer was 1 determined from the measurement values of 19 1H-NMR, 13 19F-NMR or

[0188] [Measurement of the molecular weight of the polymer] The weight average molecular weight Mw and the molecular weight dispersity (the ratio of the number average molecular weight Mn to the weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC). <00,00869>Specifically, the apparatus used was a Tosoh Corporation HLC-8320GPC. For the columns, one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) were connected in series. Polystyrene was used as the standard substance, and tetrahydrofuran (THF) was used as the developing solvent. A refractive index difference detector was used.

[0189] 1. Synthesis of fluororesins [Synthesis of Fluorine-containing Resin 1] In 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 (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St), 12.5 parts by mass of 2-(perfluorohexyl)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 6.0 parts by mass of glycerin monomethacrylate (manufactured by 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 added at room temperature (approximately 20°C). Subsequently, 2.3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (a product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) were added, and the mixture was degassed while stirring. Next, the flask was purged with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was carried out overnight. This yielded a precursor solution of fluororesin 1. After replacing the inside of the flask with dry air, the reaction mixture was cooled to an internal temperature of 60°C. Then, 0.01 parts by mass of dibutylhydroxytoluene (Tokyo Chemical Industries, Ltd.; hereinafter referred to as BHT) and 11.4 parts by mass of 2-isocyanatoethyl acrylate (Showa Denko K.K.; product name: Karenz AOI) were added to the flask. The mixture was then stirred for 4 hours. The stirred solution was cooled to room temperature (20°C) to obtain fluororesin 1.

[0190] (NMR measurement results) The composition ratio of each structural unit of the precursor of the fluororesin 1, expressed in terms of molar ratio, was: structural unit derived from BTFBE: structural unit derived from p-AcO-St: structural unit derived from MA-C6F: structural unit derived from Gly-MA = 15:18:29:38.

[0191]

Chemical formula

[0192] (GPC measurement results) Mw = 13,300 and Mw / Mn = 1.7.

[0193] [Synthesis of fluororesin 2] In a 300 mL glass flask equipped with a stirrer, at room temperature (about 20 °C), 9.5 g (0.05 mol) of BTFBE, 13.0 g (0.10 mol) of hydroxyethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as HEMA), 43.2 g (0.1 mol) of MA-C6F, 8.6 g (0.10 mol, product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MAA), 7.8 g (0.75 mol, product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as St), and 82 g of MEK were placed. Then, 1.6 g (0.005 mol) of AIBN was added, and the mixture was degassed while stirring. Next, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 75 °C and reacted for 6 hours. Thereby, a precursor solution of the fluororesin 2 was obtained. After replacing the inside of the flask with dry air, the reaction solution was cooled to an internal temperature of 60 °C, and 0.01 part by mass of dibutylhydroxytoluene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as BHT) and 12.1 parts by mass of 2-isocyanatoethyl acrylate (product of Showa Denko K.K.; product name: Karenz AOI) were added. Then, it was stirred for 4 hours. The stirred solution was cooled to room temperature (20 °C) to obtain the fluororesin 2.

[0194] (NMR measurement results) The composition ratio of each structural unit of the fluororesin precursor 2, expressed in mol%, was: structural unit derived from BTFBE : structural unit derived from HEMA : structural unit derived from MA-C6F : structural unit derived from MAA : structural unit derived from St = 15:25:30:10:20.

[0195] [Chemical formula]

[0196] (GPC measurement results) Mw = 7,200 and Mw / Mn = 1.3.

[0197] 2. Preparation of black pigment dispersion The pigment, dispersant, alkali-soluble resin, and solvent shown in the following table were mixed so as to have the mass ratio shown in the following table. This solution was subjected to dispersion treatment for 12 hours at 25°C using 0.5 mmφ zirconia beads in a bead mill. After completion of the dispersion treatment, the beads were removed by filtration. Thus, black pigment dispersion 1 was prepared.

[0198] [Table 1]

[0199] 3. Preparation of photosensitive composition The components used in the following examples and comparative examples are shown below.

[0200] [Compound having an ethylenic carbon-carbon double bond] Ethylenically unsaturated compound 1: manufactured by Nippon Kayaku Co., Ltd., DPHA (dipentaerythritol hexaacrylate) (The content of double bonds (C=C) contained in DPHA was 24.9 mass% in DPHA.)

[0201] [Thiol-based compound] Thiol compound 1: Karenz-MTPE1 (pentaerythritol tetrakis(3-mercaptobutyrate)) (a tetrafunctional secondary thiol) manufactured by Showa Denko Corporation. (The mercapto group content of pentaerythritol tetrakis(3-mercaptobutyrate) was 24.3% by mass.) Thiol compound 2: Karenz-MTBD1 (1,4-bis(3-mercaptobutyryloxy)butane), manufactured by Showa Denko Co., Ltd. (a bifunctional secondary thiol) (the mercapto group content of 1,4-bis(3-mercaptobutyryloxy)butane was 22.5% by mass). Thiol compound 3: Manufactured by SC Organic Chemical Industry Co., Ltd., DPMP (dipentaerythritol hexakis(3-mercaptopropionate)) (a hexafunctional primary thiol) (The mercapto group content of dipentaerythritol hexakis(3-mercaptopropionate) was 25.3% by mass.)

[0202] [Photoradical initiator] Photoradical initiator 1: Omnirad819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), manufactured by IGM RESINS BV.

[0203] [Alkali-soluble resin] Alkali-soluble resin 1: ZAR-2050H, manufactured by Nippon Kayaku Co., Ltd. (Special BIS-A type epoxy resin, containing the structural unit represented by the general formula (d) above)

[0204] [Fluorine resin] Fluorine-containing resin 1: Fluorine-containing resin 1 synthesized in the above "Synthesis of Fluorine-containing resin 1" Fluorine-containing resin 2: Fluorine-containing resin 2 synthesized in the above "Synthesis of Fluorine-containing resin 1" Fluorine-containing resin 3: Manufactured by DIC Corporation, MegaFac RS-72A Fluorine-containing resin 4: Neos Corporation, Futergent 601ADH2

[0205] [Coloring Pigment] Black Pigment Dispersion 1: The black pigment dispersion 1 prepared in the above "2. Preparation of Black Pigment Dispersion" White Pigment Dispersion 1: Dainichi Seika Kogyo, NX - 501 (titanium oxide pigment, pigment content: 73% by mass)

[0206] [Additive] Additive 1: Adhesion improver manufactured by Nippon Kayaku Co., Ltd., KAYAMER PM - 21

[0207] [Ultraviolet Absorbent] Ultraviolet Absorbent 1: Tinuvin 326 (manufactured by BASF, benzotriazole - based ultraviolet absorbent)

[0208] [Preparation of Photosensitive Composition] Each component was weighed so that the content ratio of the solid content of each component was the ratio described in the table shown below in the total solid content. Each weighed component was put into propylene glycol monomethyl ether acetate (PGMEA) and stirred and dissolved. The amount of PGMEA was adjusted so that the total solid content of the composition was 50% by mass. In this way, the photosensitive compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared.

[0209] 4. Evaluation [Pattern Formation] First, a substrate was prepared. Specifically, a 10 cm square ITO substrate was washed with ultrapure water and then with acetone, and then UV ozone treatment was performed for 5 minutes using a UV ozone treatment apparatus (manufactured by Sen Special Light Source Co., Ltd., model number PL17 - 110). In this way, the substrate for evaluation was obtained. Next, using a spin coater, the photosensitive composition was applied onto the substrate at a rotational speed of 300 rpm. After coating, the substrate was heated on a hot plate at 80°C for 150 seconds to dry the solvent and obtain an unexposed film. Then, using a mask aligner (product of Zeiss Microtech Co., Ltd.), the unexposed film was irradiated with i - ray (wavelength 365 nm) through a mask with a line: space = 10 μm: 10 μm. Next, the film was spray-developed for 40 seconds with a 0.04% by mass potassium hydroxide aqueous solution. After development, it was rinsed with pure water for 10 seconds, and then any remaining developer and rinse solution on the film was removed by N2 blowing. Furthermore, it was heated on a hot plate at 80°C for 60 minutes (curing treatment). A patterned cured film was obtained in the manner described above.

[0210] Using the obtained patterned cured film, we measured the sulfur content in the cured film, evaluated the partition performance (sensitivity, resolution, adhesion), and measured the contact angle.

[0211] [Sulfur content in the cured film] The sulfur content in the resulting patterned cured film was quantified using the following equipment. Combustion ion chromatography was used to quantify sulfur. Sodium sulfate was used as the calibration curve, and the sulfur content in the cured film was calculated from the sulfate ion content of the obtained calibration curve. • Combustion unit: AQF-2100H, manufactured by Mitsubishi Chemical Analytech Co., Ltd. • Ion chromatograph: DIONEX ICS5000+, manufactured by Thermo Fisher Scientific. • Columns: AG11-HC (4 x 50 mm) / AS11-HC (4 x 250 mm), manufactured by ThermoFisher Scientific. ·Eluent: KOH aqueous solution

[0212] [Sensitivity and Resolution] By varying the exposure, the optimal exposure amount (Eop(mJ / cm²)) is determined for forming a line:space = 10μm:10μm pattern on a substrate using a mask pattern with a line:space = 10μm:10μm. 2 ) was determined. In this process, the process conditions other than the exposure amount were in accordance with the description in [Pattern Formation] above. The obtained Eop value was used as an indicator of sensitivity.

[0213] Furthermore, the obtained patterns were observed under a microscope, and the resolution was evaluated according to the following criteria. • If no residue is found in the spaced area and the line edge roughness is extremely low: "Excellent" • If a small amount of residue is observed in the spaced area, and / or if a certain degree of line edge roughness is observed: "Good" • If there was significant residue in the spaced area and / or high line edge roughness: "Not acceptable"

[0214] [Anisole contact angle] (Preparation of a hardened film for measurement) First, a flat cured film (solid film) without a pattern for measuring the contact angle was created using the following procedure. (1) A 10 cm square ITO substrate was washed with ultrapure water, followed by acetone. Then, the substrate was treated with UV ozone for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Source Co., Ltd., model number PL17-110). (2) The photosensitive composition was applied to the substrate after the processing described in (1) using a spin coater at a rotation speed of 400 rpm. Then, it was heated on a hot plate at 100°C for 150 seconds. In this way, a flat cured film (solid film) with a thickness of 3 μm was created.

[0215] (Measurement of contact angle) The static contact angle of the cured film (solid film) surface obtained by the above process with respect to anisole was measured at 20 locations on the cured film using a contact angle meter (GMs-601, manufactured by Kyowa Interfacial Chemical Co., Ltd.). The average value of the measurements at the 20 locations was used to classify the static contact angle as "Excellent" if it was 60° or higher, "Good" if it was between 50 and 59°, and "Poor" if it was 49° or lower.

[0216] [Adhesion of the hardened film] The adhesion of the cured film was evaluated by observing the line:space pattern using electron microscopy and by performing a cross-cut test. Details of the evaluation method are described below.

[0217] (Observation of line:space patterns by electron microscopy) The optimal exposure amount Eop(mJ / cm²) in the above [Sensitivity and Resolution] section. 2 The line:space = 10 μm:10 μm pattern obtained by exposure evaluation was observed using an electron microscope. Within the observed area (2000 μm × 5000 μm electron microscope image), a sample was judged "good" if the area of ​​delamination was 5% or less, and "bad" if the area of ​​delamination was more than 6%.

[0218] (Cross-cut test) For compositions that received a "good" evaluation based on the electron microscope observation described above, a cross-cut test was also performed according to the following procedure. (1) A flat cured film (solid film) was obtained as described above in [Anisole Contact Angle] (Preparation of Cured Film for Measurement). (2) A grid of 25 squares (5 squares x 5 squares) of 1 mm squares was formed on the cured film using a utility knife, and it was held for one day in an environment of 121°C, 100% relative humidity, and 2 atmospheres. (3) At room temperature, commercially available cellophane tape (registered trademark) was attached to the grid area, and then the cellophane tape was peeled off. Specifically, within 5 minutes of attaching the cellophane tape, the edge of the cellophane tape was grasped, and the cellophane tape was peeled off in 0.5 to 1.0 seconds, while ensuring that the angle between the cellophane tape and the surface of the substrate on which the hardened film was formed was as close to 60° as possible.

[0219] The grid area was observed after the cellophane tape was peeled off. A "Superior" rating was given if not a single cell in the 25 squares (5x5 grid) area peeled off.

[0220] [Degree of curing (curing properties at 80°C)] The cured film obtained as described in [Pattern Formation] was immersed in propylene glycol monomethyl ether acetate for 3 minutes. The percentage change in the height of the line portion of the pattern before and after immersion was measured and used as an indicator of the degree of curing. Samples with a height change of 10% or less before and after immersion were rated "Excellent," those with a change of 10-20% were rated "Good," and those with a change of more than 20% or where pattern peeling was observed were rated "Unacceptable."

[0221] The composition and physical properties of the photosensitive composition, along with the evaluation results, are summarized in Tables 2 and 3.

[0222] [Table 2]

[0223] [Table 3]

[0224] As shown in Table 2, the photosensitive compositions of Examples 1 to 16, in which the proportion of thiol compounds in the total solids was 10% by mass or more and which did not contain UV absorbers, showed a degree of curing (curability at 80°C) of "excellent" or "good". In contrast, the photosensitive compositions of Comparative Examples 1 to 4, in which the proportion of thiol compounds in the total solids was less than 10% by mass, and the photosensitive compositions of Comparative Examples 5 and 6, which contained 3.0% by mass of UV absorbers in the total solids, showed a degree of curing (curability at 80°C) of "unacceptable". From this, it can be understood that photosensitive compositions in which the proportion of thiol compounds (B) is 10% by mass or more and which do not contain UV absorbers, or contain only a small amount, can be sufficiently cured at a relatively low temperature of around 80°C. Furthermore, the photosensitive compositions of Examples 1 to 16 exhibited desirable properties for forming partitions in light-emitting elements, in addition to their degree of curing (curability at 80°C), specifically good sensitivity, good resolution, a large anisole contact angle, and good adhesion.

[0225] A more detailed analysis of Table 2 reveals, for example, from a comparison between Example 3 and the other examples, that in terms of resolution, it is preferable to have a smaller amount of thiol compound and a smaller R value.

Claims

1. Compound (A) having an ethylenically active carbon-carbon double bond, One or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors, Photoradical initiator (C), A photosensitive composition comprising, The proportion of the thiol compound (B) in the total solid content of the photosensitive composition is 10% by mass or more. A photosensitive composition that does not contain ultraviolet absorbers, or if it does, contains less than 3% by mass of the total solids.

2. A photosensitive composition according to claim 1, The number of moles of the ethylenic carbon-carbon double bond in compound (A) is M. Ｃ＝Ｃ year, The number of moles of mercapto groups in the thiol is M ＳＨ１ M is the number of moles of mercapto groups that can be generated from the thiol precursor. ＳＨ２ In that case, R = (M ＳＨ１ +M ＳＨ２ ) / M Ｃ＝Ｃ A photosensitive composition having a value of 0.30 to 8.

50.

3. A photosensitive composition according to claim 1 or 2, A photosensitive composition in which R is 0.50 to 2.

50.

4. A photosensitive composition according to claim 1 or 2, Furthermore, a photosensitive composition containing an alkali-soluble resin (D).

5. A photosensitive composition according to claim 1 or 2, A photosensitive composition further containing a fluororesin (E).

6. A photosensitive composition according to claim 1 or 2, A photosensitive composition further containing a coloring agent (F).

7. A photosensitive composition according to claim 1 or 2, A photosensitive composition used to form partitions in light-emitting elements.

8. A film-forming step of forming a film by coating a substrate with the photosensitive composition according to claim 1 or 2, An exposure step of pattern exposure of the aforementioned film, The developing process involves developing the film after exposure, A heating process in which the film after development is heated and hardened, A method for producing a resin-cured film having the following characteristics.

9. A method for producing a resin cured film according to claim 8, A method for manufacturing a resin-cured film, wherein in the heating step, the developed film is heated to 50 to 150°C.

10. A method for producing a resin cured film according to claim 8, A method for manufacturing a resin-cured film, wherein in the heating step, the developed film is heated to 50 to 100°C.

11. A method for producing a resin cured film according to claim 8, A method for producing a resin-cured film, wherein the film-forming step involves heating the coated photosensitive composition at 50 to 150°C.

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

13. A partition according to claim 12, A partition wall for light-emitting elements.

14. A light-emitting element comprising a partition wall as described in claim 12, and a light-emitting layer or wavelength conversion layer disposed in a region partitioned by the partition wall.

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

Images