Container containing curable composition, method for producing cured film, pattern, light-emitting element, display device, and method for producing curable composition

Abstract

Provided is a container containing a curable composition. A curable composition containing a compound having an ethylenic carbon-carbon double bond, one or more thiol-based compounds selected from the group consisting of thiol and thiol precursor, and a radical initiator, and an oxygen-containing gas are sealed in the container having a sealing capability. Moreover, provided is a method for producing a curable composition, the method comprising: a preparation step for preparing a mixture by mixing a compound having an ethylenic carbon-carbon double bond, one or more thiol base compounds selected from the group consisting of thiol and thiol precursor, and a radical initiator; and an oxygen contact step for bringing the mixture in contact with an oxygen-containing gas.

Description

Container containing curable composition, method for producing cured film, pattern, light-emitting element, display device, and method for producing curable composition

[0001] The present invention relates to a container containing a curable composition, a method for producing a cured film, a pattern, a light-emitting device, a display device, and a method for producing a curable composition.

[0002] BACKGROUND ART Due to the industrial importance and wide range of application fields of curable compositions such as negative curable compositions, various improvements are being continuously investigated.

[0003] As an example, Patent Document 1 describes a negative photosensitive resin composition that contains an alkali-soluble resin or an alkali-soluble monomer having an ethylenic double bond, a photopolymerization initiator, a thiol compound having three or more mercapto groups in one molecule, and an ink repellent agent, as a composition that can be preferably used for forming partition walls of optical elements.

[0004] As another example, Patent Document 2 describes a curable composition (negative type) containing at least an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and at least one compound having two or more chain-transferable substituents (specifically, a thiol compound).

[0005] International Publication No. 2014 / 084279 Japanese Patent Application Laid-Open No. 2006-285174

[0006] In practice, curable compositions are sometimes required to have minimal changes in properties due to storage. It is preferable that the properties of a curable composition remain substantially unchanged between immediately after production and after some time has passed since production. A curable composition with minimal changes in properties due to storage can be produced in large quantities and stockpiled. This leads to a reduction in the production cost of the curable composition. Furthermore, by using a curable composition with minimal changes in properties due to storage in the production of a product, it becomes easier to produce products of consistent quality, and an improvement in product yield can be expected. However, based on the findings of the present inventors, there is room for improvement in the changes in properties of conventional curable compositions due to storage.

[0007] The present invention has been made in view of the above circumstances, and one of the objects of the present invention is to reduce the change in properties of a curable composition during storage.

[0008] The present inventors have completed the invention provided below and solved the above problems.

[0009] 1. A container containing a curable composition, the container comprising: a curable composition comprising a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator; and an oxygen-containing gas, all sealed in a hermetically sealed container. 2. The container containing the curable composition according to 1., wherein the volume of the oxygen-containing gas is 3 to 50% by volume of the volume of the container. 3. The container containing the curable composition according to 1. or 2., wherein the oxygen concentration of the oxygen-containing gas is 1 to 100% by volume. 4. The container containing the curable composition according to 1. or 2., wherein the oxygen concentration of the oxygen-containing gas is 20 to 25% by volume. 5. The container containing the curable composition according to any one of 1. to 4., wherein the pressure of the oxygen-containing gas is 0.5 to 1.5 atm. 6. A container containing a curable composition according to any one of 1. to 5., wherein the oxygen-containing gas comprises at least one selected from the group consisting of nitrogen gas and noble gases. 7. A container containing a curable composition according to any one of 1. to 6., wherein the surface of the sealable container that comes into contact with the curable composition is made of resin. 8. A container containing a curable composition according to any one of 1. to 7., wherein the sealable container has light-blocking properties. 9. A container containing a curable composition according to any one of 1. to 8., wherein the radical initiator comprises a photoradical initiator. 10. A container containing a curable composition according to any one of 1. to 9., wherein the curable composition comprises a disulfide compound. 11. A container containing a curable composition according to any one of 1. to 10. 11. A container containing the curable composition according to any one of items 1 to 11, wherein the curable composition further comprises an alkali-soluble resin. 12. A container containing the curable composition according to any one of items 1 to 11, wherein the curable composition further comprises a fluorine-containing resin.13. A container containing a curable composition according to any one of 1. to 12., wherein the curable composition further contains a colorant. 14. A container containing a curable composition according to any one of 1. to 13., wherein the viscosity of the curable composition in the container containing the curable composition, measured using a Brookfield viscometer, is η. ０ The container containing the curable composition is stored at 40°C for 7 days, and the viscosity of the curable composition in the container containing the curable composition measured using a Brookfield viscometer is defined as η １ When this is done, (|η １ -η ０ | / η ０) × 100(%) × 100(%) is 15% or less. 15. A container containing a curable composition according to any one of 1. to 14., wherein the curable composition in the container is used to form a partition wall in a light-emitting device. 16. A method for producing a cured film, comprising: a film-forming step of applying the curable composition in the container containing the curable composition according to any one of 1. to 15. onto a substrate to form a film; and a heating step of heating and curing the film. 17. A pattern composed of a cured product of the curable composition in the container containing the curable composition according to any one of 1. to 15.. 18. The pattern according to 17., wherein the pattern is used as a partition wall in a light-emitting device. 19. A light-emitting device comprising the pattern according to 17. or 18., and a light-emitting layer or a wavelength conversion layer arranged in a region defined by the pattern. 20. 19. 21. A display device comprising the light-emitting element described in 2. 21. A method for producing a curable composition, comprising: a preparation step of mixing a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator to prepare a mixture; and an oxygen contact step of contacting the mixture with an oxygen-containing gas. 22. A method for producing a curable composition according to 21., wherein the oxygen contact step is carried out for 1 to 180 days. 23. A method for producing a curable composition according to 21. or 22., wherein the oxygen contact step is carried out at 3 to 35°C. 24. A method for producing a curable composition according to any one of 21. to 23., comprising a degassing step of degassing dissolved gas in the mixture between the preparation step and the oxygen contact step.

[0010] According to the present invention, it is possible to reduce changes in the properties of a curable composition during storage.

[0011] 1 is a diagram (schematic cross-sectional view) for explaining a container containing a curable composition. FIG. 2 is a diagram for explaining a container containing a curable composition (different from the one shown in FIG. 1 ).

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all drawings, similar components are given the same reference numerals, and descriptions thereof will be omitted where appropriate. To avoid complexity, (i) when multiple identical components are present in the same drawing, only one of the components is given a reference numeral, and not all of the components are given a reference numeral, or (ii) particularly in Figure 2 and subsequent figures, components similar to those in Figure 1 are not given a reference numeral again. All drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual objects.

[0013] In this specification, the notation "X to Y" in the description of a numerical range means X or more and Y or less, unless otherwise specified. For example, "1 to 5 mass %" means "1 mass % or more and 5 mass % or less." In the notation of groups (atomic groups) in this specification, notations that do not specify whether they are substituted or unsubstituted include both unsubstituted and substituted groups. For example, the term "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, the notation "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate." In this specification, the term "organic group" refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

[0014] <Container with Curable Composition> FIG. 1 is a schematic diagram showing a cross section of a container with a curable composition according to this embodiment. The container with the curable composition comprises, for example, a container body 1, a lid 3 capable of closing the opening of the container body 1, a curable composition 5 contained within the container body 1, and an oxygen-containing gas 7 filling the portion of the container body 1 not occupied by the curable composition 5. The combination of the container body 1 and the lid 3 provides a hermetic seal for the container as a whole. In other words, by properly closing the opening of the container body 1 with the lid 3, the inflow of substances from the outside and the outflow of substances from the inside are sufficiently suppressed. Note that, as long as there is no problem in terms of performance, small amounts of unavoidable inflow / outflow of substances are permitted. The curable composition 5 includes a compound having an ethylenic carbon-carbon double bond, one or more thiol-based compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator. The lid 3 is usually closed during storage of the curable composition 5. That is, during storage of the curable composition 5, the curable composition and the oxygen-containing gas are sealed in a hermetically sealed container.

[0015] In a container containing the curable composition, the curable composition is in contact with an oxygen-containing gas. This is thought to reduce changes in the properties of the curable composition during storage. Based on the results of the inventors' studies, it is speculated that a disulfide compound produced by the reaction of oxygen in the oxygen-containing gas with a thiol compound in the curable composition inhibits deterioration of the curable composition.

[0016] The mechanism by which disulfide compounds suppress deterioration of curable compositions can be considered as follows. Radicals unintentionally generated in the curable composition, particularly radicals generated by unintentional decomposition of a radical initiator, react with a thiol compound to generate S radicals. The generated S radicals react with disulfide compounds faster than they react with compounds having ethylenic carbon-carbon double bonds, generating different S radicals. These radicals further react with disulfide compounds, thereby suppressing the reaction with compounds having ethylenic carbon-carbon double bonds. Incidentally, it is assumed that the generated radicals are deactivated at a certain rate.

[0017] In this embodiment, disulfide compounds are not added to the curable composition, but are generated by the action of oxygen in contact with the curable composition. This is thought to result in the disulfide compounds being generated "little by little" and "continuously." Such generation of disulfide compounds may be effective in maintaining the properties of the curable composition over the long term.

[0018] Just to be clear, the above description of the presumed mechanism etc. includes presumptions, and the present invention is not limited to the above description.

[0019] For reference, when filling a container with a curable composition, the void space within the container has traditionally been filled with an inert gas such as nitrogen gas or a noble gas to prevent deterioration. Alternatively, to avoid contact with oxygen, the container has also been filled with the curable composition at a 100% filling rate. In contrast to these conventional techniques, the present embodiment is surprising in that it brings oxygen, which is considered the most common substance that deteriorates curable compositions, into contact with the curable composition, and is based on the unique insight of the present inventors. Intentionally providing void space within a container where no curable composition is present means that more containers are required when storing or transporting a certain amount of curable composition. In other words, this embodiment sacrifices costs such as the cost of the container itself and the cost of transporting the container containing the curable composition. However, suppressing changes in the properties of the curable composition during storage and transportation is necessary to improve the reliability of the curable composition. Of the various factors considered when industrially using a curable composition, this embodiment particularly emphasizes suppressing changes in the properties of the curable composition during storage and transportation.

[0020] The container containing the curable composition exemplified in FIG. 1 will now be described in more detail.

[0021] [Container Body 1 and Lid 3] The container body 1 and lid 3 are not particularly limited as long as they can sufficiently prevent substances such as gases from entering the container body 1 and from escaping from the container body 1 when the curable composition 5 is placed in the container body 1 and the lid 3 is closed. Ideally, no substances such as gases enter or leave the container. However, as long as changes in the properties of the curable composition are suppressed, small, unavoidable amounts of substances such as gases are permitted.

[0022] The materials of the container body 1 and the lid 3 are not particularly limited. Any material can be used as long as it is not substantially attacked by the curable composition 5. The materials of the container body 1 and the lid 3 may be the same or different. At least the surfaces of the container body 1 and the lid 3 that come into contact with the curable composition 5 are preferably made of a resin. Examples of resins include polyolefins such as polyethylene and polypropylene, polycycloolefins, polystyrene, and polycarbonate. Substantially the entire container body 1 and the lid 3 may be made of a resin. The inner walls of one or both of the container body 1 and the lid 3 may be lined with a resin such as a fluororesin. Specifically, the outer surfaces of the container body 1 and the lid 3 may be made of a metal such as iron or stainless steel, and the inner walls of the container body 1 and the lid 3 may be lined with a resin.

[0023] The container body 1 and the lid 3 preferably have light-blocking properties. When the curable composition is photosensitive, the light-blocking properties of the container body 1 and the lid 3 can further prevent deterioration of the curable composition. Also, when the curable composition is non-photosensitive, the use of a container with light-blocking properties tends to prevent deterioration of the curable composition. For example, Sanplatec Co., Ltd. sells a polyethylene container with light-blocking properties that is suitable for storing curable compositions. Furthermore, the container body 1 and / or the lid 3 may have a metal outer surface to prevent light from reaching the curable composition contained therein.

[0024] The volume of the container body 1 is preferably 0.1 to 200 L, more preferably 0.5 to 200 L, and even more preferably 3 to 200 L, from the viewpoint of the amount of curable composition that can be carried at one time and handling properties.

[0025] [Curable Composition 5] As described above, the curable composition 5 contains a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator. The curable composition 5 may contain any component other than these. The curable composition 5 may be non-photosensitive (thermosetting) or photosensitive. The following mainly describes components that can be contained in the curable composition 5 when the curable composition 5 is photosensitive.

[0026] (Compound (A) Having an Ethylenic Carbon-Carbon Double Bond) The curable composition 5 contains a compound (A) having an ethylenic carbon-carbon double bond. Hereinafter, the compound (A) having an ethylenic carbon-carbon double bond may be simply referred to as compound (A).

[0027] As the compound (A), any compound having an ethylenic carbon-carbon double bond can be used without any particular limitation. The term "ethylenic carbon-carbon double bond" refers to a carbon-carbon double bond that can react by the action of a radical. Conjugation-stabilized double bonds such as the double bond of a benzene ring do not fall under the category of "ethylenic carbon-carbon double bond." From the viewpoint of improving reactivity, it is preferable that the compound (A) has an ethylenic carbon-carbon double bond at its terminal.

[0028] The compound (A) may be monofunctional or polyfunctional. That is, the compound (A) may have only one ethylenic carbon-carbon double bond per molecule, or may have two or more (specifically, 2 to 8, more specifically, 2 to 6) ethylenic carbon-carbon double bonds per molecule. From the viewpoints of further improving sensitivity and improving the physical properties of a cured film, it is preferable that the compound (A) is polyfunctional.

[0029] The compound (A) is preferably a (meth)acrylate compound, that is, a compound having a (meth)acryloyl group as a structure containing an ethylenic carbon-carbon double bond, and more preferably a (meth)acrylate compound.

[0030] Specific examples of the compound (A) include the following: Of course, the compound (A) is not limited to these.

[0031] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; urethane (meth)acrylates obtained by reacting polyisocyanate with a hydroxy group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, etc.

[0032] The curable composition 5 may contain only one compound (A) or may contain two or more compounds (A). The content of the compound (A) is usually 5 to 60 mass%, preferably 10 to 55 mass%, and more preferably 15 to 50 mass%, of the total non-volatile components of the curable composition 5. The content of double bonds (C═C) in the compound (A) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and more preferably 10 to 30 mass%.

[0033] (Thio-based compound (B)) The curable composition 5 contains one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors. Hereinafter, one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors may be simply referred to as thiol-based compounds (B).

[0034] The thiol compound (B) may be monofunctional or polyfunctional. That is, the thiol compound (B) may have only one mercapto group (or latent mercapto group) per molecule, or may have two or more (specifically, 2 to 8) mercapto groups (or latent mercapto groups) per molecule. From the viewpoint of improving the physical properties of a cured film, the thiol compound (B) is preferably polyfunctional.

[0035] Specific examples of the thiol in the thiol compound (B) include those represented by the following general formula (b).

[0036]

[0037] In the general formula (b), R is a hydrogen atom, an alkyl group, or a cycloalkyl group, and X is —CO— or —CH ２ -, L is an n-valent linking group, and n is an integer of 2 or more, preferably 2 to 8, more preferably 2 to 6. Multiple Rs may be the same or different from each other. Furthermore, multiple Xs may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that multiple Rs are the same as each other, and it is preferable that multiple Xs are the same as each other.

[0038] The alkyl group for R may be linear or branched. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. Of these, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0039] Examples of L, which is an n-valent linking group, include a linear or branched alkylene chain (having, for example, 2 to 6 carbon atoms), a trimethylolpropane residue, -(CH ２ ) ｐExamples include trivalent linking groups such as an isocyanuric ring having three - (p is 2 to 6), tetravalent or pentavalent linking groups such as a pentaerythritol residue, and hexavalent linking groups such as a dipentaerythritol residue.

[0040] Commercially available thiols in the thiol compound (B) include, for example, the "Karens" series manufactured by Showa Denko K.K. The thiols in this series are secondary thiols. Other examples include products sold by SC Organic Chemical Co., Ltd. under product numbers PEMP, TMMP, DPMP, and TEMPIC. These thiols are primary thiols. Generally, primary thiols are more reactive and may be more advantageous in terms of low-temperature curing. However, as shown in the examples below, it is possible to obtain satisfactory results even with secondary thiols. Incidentally, secondary thiols may suppress the reactivity of the thiol group due to steric hindrance, potentially improving the stability of the composition.

[0041] The "thiol precursor" in the thiol compound (B) refers to a compound that does not itself have a mercapto group, but generates a mercapto group in the composition upon physical stimulation or chemical action. The thiol precursor can be, for example, a thioester, a dithioester, a thiocarbamate, a dithiocarbamate, a thiocarbonate, a xanthogenate, or a trithiocarbonate. The specific structure of the thiol precursor can be, for example, one in which the —SH moiety in the above general formula (b) is esterified or formed into a salt. Thiol precursors are described, for example, in JP-A-2004-517979.

[0042] The content of mercapto groups in the thiol compound (B) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and more preferably 10 to 30 mass%, based on the molecular weight of the thiol compound (B). When the thiol compound (B) is a thiol precursor, this value is calculated based on the chemical structure after the thiol precursor is converted into the thiol compound.

[0043] The curable composition 5 may contain only one thiol-based compound (B), or may contain two or more thiol-based compounds (B).

[0044] The content of the thiol compound (B) is not particularly limited, but in one embodiment, it is, for example, 0.1 to 10 mass%, specifically 0.5 to 8 mass%, more specifically 1 to 5 mass%, and even more specifically 1 to 3 mass%, of the total non-volatile components of the curable composition 5. The content of the thiol compound (B) is, for example, 0.2 to 25 mass parts, specifically 1 to 20 mass parts, and more specifically 2 to 15 mass parts, relative to 100 mass parts of the compound (A). Incidentally, when the thiol compound (B) is used in such an amount, it is believed that the thiol compound (B) functions primarily as a chain transfer agent and is involved in adjusting the chain length of the polymer produced by the radical polymerization reaction of the compound (A).

[0045] In another embodiment, the content of the thiol-based compound (B) is typically 10 to 70 mass%, preferably 15 to 60 mass%, and more preferably 20 to 55 mass% of the total non-volatile components of the curable composition 5. The content of the thiol-based compound (B) is, for example, 30 to 80 mass parts, specifically 30 to 70 mass parts, and more specifically 35 to 70 mass parts, relative to 100 mass parts of the compound (A). When the thiol-based compound (B) is used in this amount, the curable composition 5 is believed to cure primarily through the thiol-ene reaction, which is known as a bond-forming reaction between a thiol and an alkene. Depending on the ratio of the compound (A) to the thiol-based compound (B), both the radical polymerization reaction of the compound (A) and the thiol-ene reaction may occur.

[0046] (Radical initiator (C)) The curable composition 5 contains a radical initiator (C). As the radical initiator (C), a thermal radical initiator that generates radicals by heat, or a photoradical initiator that generates radicals by irradiation with light (typically ultraviolet light such as i-rays) can be used without any particular limitation.

[0047] Specific examples of thermal radical initiators include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butyl peroxybenzoate, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters, and organic peroxides such as percarbonates. Other examples include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile). Incidentally, some of the photoradical initiators specifically described below generate radicals upon heating. Therefore, the photoradical initiators specifically described below may also be used as thermal radical initiators.

[0048] Specific examples of photoradical initiators include intramolecular cleavage initiators in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction initiators in which radicals are generated by using a hydrogen donor such as a tertiary amine or ether in combination. Any of these may be used in this embodiment. Of course, photoradical initiators other than these may also be used.

[0049] Specific examples of the photoradical initiator include oxime ester-based, benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based photoradical initiators.

[0050] Specific examples of the oxime ester photoradical initiator include CGI-325 manufactured by BASF, IRGACURE OXE01 (1-[4-(phenylthio)phenyl]-1,2-octadione-2-(o-benzoyloxime), IRGACURE OXE02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(o-acetyloxime)]), and N-1919 manufactured by ADEKA Corporation.

[0051] Specific examples of the benzophenone-based photoradical initiator include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0052] Specific examples of the acetophenone-based photoradical initiator include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0053] Specific examples of the diketone-based photoradical initiator include 4,4'-dimethoxybenzyl, methyl benzoylformate, 9,10-phenanthrenequinone, etc. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0054] Specific examples of the acylphosphine oxide initiator include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0055] Specific examples of the quinone initiator include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0056] Specific examples of the acyloin initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Among these, benzoin and benzoin methyl ether are preferred.

[0057] Among commercially available photoradical initiators, preferred ones include BASF's product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04, Darocur 1173, and Lucirin TPO; and Tronly's product name: TR-PBG-305.

[0058] The curable composition 5 may contain only one radical initiator (C), or may contain two or more radical initiators (C). The content of the radical initiator (C) may be adjusted appropriately, taking into consideration sufficient curability and other factors. The content of the radical initiator (C) is typically 0.1 to 10 mass%, preferably 0.3 to 8 mass%, and more preferably 0.5 to 5 mass%, of the total non-volatile components of the curable composition 5. From another perspective, the amount of the radical initiator (C) relative to 100 parts by mass of the compound (A) is typically 0.2 to 25 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass.

[0059] (Alkali-Soluble Resin (D)) The curable composition 5 preferably contains an alkali-soluble resin (D). Use of the alkali-soluble resin (D) tends to facilitate the formation of a pattern of a desired shape, particularly when forming a pattern (partition wall) using an alkali developer. The alkali-soluble resin (D) typically has an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group and a phenolic hydroxy group. In this specification, a resin that has a fluorine atom and is alkali-soluble is usually classified as a fluorine-containing resin (E) described below. In other words, the alkali-soluble resin (D) usually does not have a fluorine atom.

[0060] The alkali-soluble resin (D) may be, for example, an alkali-soluble novolak resin, which can be obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst. Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more. Specific examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

[0061] Examples of the alkali-soluble resin (D) include alkali-soluble epoxy resins and acid-modified epoxy (meth)acrylate resins derived from epoxy resins. The epoxy resins or acid-modified epoxy (meth)acrylate resins may have polymerizable substituents such as hydroxyl groups or (meth)acryloyl groups in their side chains. Examples of epoxy resins include bisphenol-type epoxy resins, and examples of acid-modified epoxy (meth)acrylate resins include those obtained by reacting bisphenol-type epoxy resins with (meth)acrylic acid. Specific examples include bisphenol-type epoxy resins or acid-modified epoxy (meth)acrylate resins having a structural unit represented by the following general formula (d):

[0062]

[0063] In general formula (d), two R's each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and Z represents a monovalent organic group or a hydrogen atom, provided that in at least some of the structural units represented by general formula (d) in the alkali-soluble resin (D), Z is a monovalent organic group having a carboxy group.

[0064] When R is a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 carbon atoms, specific examples of R include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group is preferred from the viewpoint of availability. Specific examples of linear perfluoroalkyl groups having 1 to 3 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Of these, a trifluoromethyl group is preferred from the viewpoint of availability. Each R may have the same structure or different structures.

[0065] When Z is a monovalent organic group, Z is preferably an alkyl group having 1 to 10 carbon atoms. This alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. At least one hydrogen atom in the monovalent organic group of Z may be substituted with a carboxy group or a hydroxy group. This increases alkali solubility.

[0066] The carboxyl group or hydroxyl group of the alkyl group having 1 to 10 carbon atoms represented by Z may be reacted with an esterifying agent. Examples of esterifying agents include acid halides, acid anhydrides, and condensing agents. When Z is a hydrogen atom, -O-Z may be reacted with an esterifying agent. Examples of esterifying agents include the same esterifying agents described above. Examples of acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, and 1,2,3,4-tetrahydrophthalic anhydride. Reacting these acid anhydrides with a resin can introduce ethylenically unsaturated bonds and carboxyl groups into the resin. The amount of carboxyl groups or hydroxyl groups in the alkali-soluble resin to be reacted with the acid anhydride may be appropriately adjusted, taking into account the solubility in alkali required for the alkali-soluble resin.

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

[0068] In addition, alkali-soluble epoxy resins or acid-modified epoxy (meth)acrylate resins other than those mentioned above can also be used. Specific examples include alkali-soluble novolac-type epoxy resins, biphenyl-type epoxy resins, and acid-modified epoxy (meth)acrylate resins derived from these epoxy resins. Commercially available acid-modified epoxy (meth)acrylates can also be used. Examples of commercially available acid-modified epoxy acrylates that can be used include those manufactured by Nippon Kayaku Co., Ltd. under the product names: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H.

[0069] The alkali-soluble resin (D) may have a polycyclic aromatic skeleton such as a fluorene skeleton. The use of such an alkali-soluble resin (D) may improve the heat resistance and durability of the cured pattern. Specific examples of the acid-modified epoxy (meth)acrylate resins described above may include those having a polycyclic aromatic skeleton, or resins having a polycyclic aromatic skeleton may be selected from a different family of resins than the acid-modified epoxy (meth)acrylate resins. Incidentally, resins having a fluorene skeleton are sometimes referred to as "cardo resins." Like other alkali-soluble resins (D), alkali-soluble resins (D) having a polycyclic aromatic skeleton such as a fluorene skeleton preferably have an alkali-soluble group such as a carboxy group or a hydroxy group.

[0070] The alkali-soluble resin (D) may have an ethylenic carbon-carbon double bond. It is believed that the alkali-soluble resin (D) having an ethylenic carbon-carbon double bond forms a bond with the compound (A) during curing of the composition and is incorporated into the cured product. This is believed to contribute to improving the stability and heat resistance of the cured product. Just to be clear, the alkali-soluble resin having an ethylenic carbon-carbon double bond is not classified as the compound (A).

[0071] The weight average molecular weight of the alkali-soluble resin (D) is preferably 1,000 to 50,000 from the viewpoint of the alkali solubility and resolution of the curable composition 5. The acid value of the alkali-soluble resin (D) (the number of milligrams of potassium hydroxide required to neutralize 1 g of sample) can be an indicator of alkali solubility. In this embodiment, the acid value of the alkali-soluble resin (D) is preferably 20 to 80, more preferably 30 to 70, and even more preferably 40 to 60. The acid values ​​of the alkali-soluble resins used in the examples described below are on this order.

[0072] When an alkali-soluble resin (D) is used, only one alkali-soluble resin (D) may be used, or two or more alkali-soluble resins (D) may be used. When an alkali-soluble resin (D) is used, the amount thereof is usually 10 to 70 mass %, preferably 15 to 60 mass %, and more preferably 20 to 55 mass %, of the total non-volatile components of the curable composition 5.

[0073] (Fluorine-Containing Resin (E)) The curable composition 5 preferably contains a fluorine-containing resin (E). By forming a pattern having concaves and convexes (partition walls of an optical element) using the curable composition 5 containing the fluorine-containing resin (E), the resulting pattern (partition walls of an optical element) becomes more likely to repel ink for forming an organic layer. This contributes to preventing ink dropped into a certain depression from "crawling" up the side surface of the depression and entering an adjacent depression. In other words, it is possible to prevent unintended mixing of dyes between pixels in an optical element.

[0074] There are no particular restrictions on the fluorine-containing resin (E) that can be used. Preferred fluorine-containing resins (E) that can be used are described below. The fluorine-containing resin (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).

[0075]

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

[0077]

[0078] In the general formula (2), two Rf's each independently represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or a fluorine atom; １ represents a hydrogen atom, a fluorine atom or a methyl group; R ２ represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0079] In general formula (2), R １ is preferably a hydrogen atom or a methyl group. ２ Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group. A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred, and a hydrogen atom and a methyl group are more preferred.

[0080] Rf in general formula (1) or general formula (2) is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, an n-nonafluorobutyl group, an isononafluorobutyl group, or a tert-nonafluorobutyl group, more preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, or a hexafluoroisopropyl group, and particularly preferably a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

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

[0082] The content of the structural unit represented by general formula (2) in the fluorine-containing resin (E) is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration solubility in solvents, resistance to various treatments in the production of light-emitting elements, and the like.

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

[0084]

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

[0086] In the general formula (3), W １represents a divalent linking group. Preferably represents -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W １ However, the group —O—C(═O)—NH— is preferable because it provides better liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element.

[0087] In general formula (3), A １ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0088] Divalent Linking Group A １ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0089] Divalent Linking Group A １ When is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0090] Divalent Linking Group A １ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0091] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, and a hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0092] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group exemplified above is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0093] Among them, the divalent linking group A １ is a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group and a 2-hydroxy-n-propylene group are particularly preferred.１ As for -C(CH ２ -) ２ CH ３ and the like, and the tetravalent linking group A １ As for C(CH ２ -) ４ Examples include:

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

[0095] In general formula (3), u represents an integer of 1 to 3, and u is particularly preferably 1. In general formula (3), n represents an integer of 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are each independently ortho-, meta-, or para-positions, and preferably para-positions. １ may be the same or different. １ may be the same or different. １ may be the same or different. ４ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of W １ are preferably the same as each other, and a plurality of A １ are preferably the same, and a plurality of Y １ are preferably the same, and a plurality of R ４ are preferably the same as each other.

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

[0097] The content of the structural unit represented by general formula (3) in the fluorine-containing resin (E) is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration solubility in solvents, resistance to various treatments in the production of light-emitting devices, and the like.

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

[0099]

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

[0101] In formula (4), W ２ represents a divalent linking group, preferably -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W ２ is preferably —O—C(═O)—NH—, since the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element is superior.

[0102] In general formula (4), A ２ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ In the general formula (4), A ３ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group can be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0103] Divalent Linking Group A ２ , A ３ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0104] Divalent Linking Group A ２ , A ３ When each of the groups independently represents a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0105] Divalent Linking Group A ２ , A ３ When each of the groups independently represents a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0106] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0107] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0108] Among them, the divalent linking group A ２ , A ３ each independently represents a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ The trivalent linking group A3 is particularly preferably —C(CH ２ -) ２ CH ３ The tetravalent linking group A3 can be C(CH ２ -) ４ Examples include:

[0109] In the general formula (4), Y ２ , Y ３ each independently represents a divalent linking group, and is preferably —O— or —NH—, and more preferably —O—.

[0110] In the general formula (4), n represents an integer of 1 to 3. It is particularly preferable that n is 1. ３ may be the same or different. ６ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of Y ３ are preferably the same, and a plurality of R ６ are preferably the same as each other.

[0111] In the general formula (4), r represents 0 or 1. When r is 0, it is represented by "(-C(=O)-)". ｒ represents a single bond.

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

[0113] The content of the structural unit represented by general formula (4) in the fluorine-containing resin (E) is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration the solubility in a solvent and the adhesion of the pattern (partition wall) to a substrate.

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

[0115]

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

[0117] In general formula (5), R ８ represents a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, in which any number of hydrogen atoms are substituted with fluorine atoms, and the fluorine content in the structural unit is 30 mass% or more.

[0118] R ８When is a linear hydrocarbon group, specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a linear alkyl group having 10 to 14 carbon atoms in which any number of hydrogen atoms have been substituted with fluorine atoms.

[0119] R ８ When is a linear hydrocarbon group, the structural unit represented by general formula (5) is preferably a structural unit represented by the following general formula (5-1):

[0120]

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

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

[0123] In the general formula (5-1), p is an integer of 1 to 4, and q is an integer of 1 to 14. It is particularly preferable that p is an integer of 1 or 2, and q is an integer of 2 to 8.

[0124] Specific preferred examples of the structural unit represented by general formula (5) include the structures described in paragraphs 0125 to 0128 of WO 2021 / 235541.

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

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

[0127]

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

[0129] In the general formula (6), each B independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or —C(═O)—O—R １１ (R １１ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, in which any number of hydrogen atoms are substituted with fluorine atoms; R １１ the fluorine content in the compound is 30% by mass or more) or —O—C(═O)—R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. In addition, m represents an integer of 0 to 3.

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

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

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

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

[0134]

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

[0136] In general formula (7), A ４ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0137] Divalent Linking Group A ４ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0138] Divalent Linking Group A ４ When is a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.

[0139] Divalent Linking Group A ４ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0140] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0141] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0142] Among them, the divalent linking group A ４ is a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)—) is particularly preferred.

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

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

[0145] In general formula (7), E １ represents a hydroxy group, a carboxyl group, or an oxirane group. １ When is an oxirane group, examples include an ethylene oxide group, a 1,2-propylene oxide group, a 1,3-propylene oxide group, etc. Among these, an ethylene oxide group is preferred.

[0146] In the general formula (7), s represents 0 or 1. When s is 0, (-Y ４ -A ４ When r is 0 and s is 0, the main chain of the structural unit does not contain E １ The resulting structure is a bonded structure.

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

[0148] The weight average molecular weight of the fluororesin (E), measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000. Adjusting the molecular weight of the fluororesin (E) may make it possible to increase the strength of the pattern (partition walls) to be formed or to increase the solubility in solvents and thereby improve coatability.

[0149] The polydispersity (Mw / Mn) of the fluororesin (E) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, particularly preferably from 1.01 to 3.00.

[0150] The fluororesin (E) may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer. From the viewpoint of dispersing the respective properties appropriately rather than locally, a random copolymer is preferred.

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

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

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

[0154] (Colorant (F)) The curable composition 5 can contain a colorant (F). As one example, the colorant (F) is used to make the resulting pattern (partition wall) black. The black pattern (partition wall) can serve as a partition wall between pixels in a light-emitting element. As another example, the colorant (F) is used to make the resulting pattern (partition wall) white, thereby increasing the reflectance of the pattern (partition wall). Naturally, an appropriate colorant (G) may be selected so as to obtain a pattern that is neither black nor white, depending on various purposes.

[0155] As the colorant (F), a pigment or a dye may be used. If necessary, a plurality of colorants may be used in combination. Incidentally, when the resulting pattern (partition wall) is to be black, a black pigment such as carbon black may be used, or a plurality of non-black pigments may be mixed to obtain a substantially black color. When the resulting pattern (partition wall) is to be gray, a black pigment and a white pigment may be mixed to obtain a gray color. As the pigment, it is preferable to use an organic pigment.

[0156] Specific examples of the colorant (F) include known colorants such as perylene pigments, lactam pigments, azo pigments, phthalocyanine pigments, carbon pigments such as carbon black, and metal oxide pigments such as iron black and titanium oxide.

[0157] The white pigment is preferably at least one inorganic substance selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. These inorganic substances have a high refractive index and therefore tend to improve the light reflectivity of the partition walls that are formed. Titanium oxide is particularly preferred from the viewpoints of its high refractive index and good dispersibility in the composition.

[0158] As other color pigments, various organic pigments such as yellow, orange, blue, red, green, purple, and brown can be used. A pigment dispersion containing two or more organic pigments may also be used. Optical properties such as solubility and light-blocking properties can be controlled by adjusting the type and amount ratio of the pigments used. In particular, a combination of blue, purple, and orange is preferred from the viewpoints of compatibility and uniformity of optical density.

[0159] Examples of organic orange pigments include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among these, C.I. Pigment Orange 43 is preferred from the viewpoints of dispersibility and light-blocking properties.

[0160] Examples of organic blue pigments include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, and 80. Among these, C.I. Pigment Blue 60 is preferred from the viewpoints of dispersibility and light-shielding properties.

[0161] Examples of organic purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, C.I. Pigment Violet 23 is preferred from the viewpoints of dispersibility and light-blocking properties.

[0162] When a pigment is used as the colorant (F), it is preferable that the pigment has been subjected to a dispersion treatment. The pigment can be dispersed, for example, by treating the pigment, dispersant, and, if necessary, solvent using a bead mill. The type of dispersant is not particularly limited, and dispersants available from BYK Corporation can be used, for example. Furthermore, when dispersing the pigment to produce a pigment dispersion in which the pigment is dispersed in a solvent (usually an organic solvent), an alkali-soluble resin may also be used. Since pigments are difficult to remove with an alkaline developer and tend to remain as development residues, the inclusion of an alkali-soluble resin in the pigment dispersion can be expected to reduce development residues. Specific alkali-soluble resins that can be used include those specifically listed above as the alkali-soluble resin (D).

[0163] When a colorant (F) is used, only one colorant (F) may be used, or two or more colorants (F) may be used in combination. When a colorant (F) is used, the amount thereof may be appropriately adjusted taking into account the balance between obtaining the sufficient effect of using the colorant (F) and the patterning properties, developability, and strength of the resulting pattern (partition wall). Specifically, when a colorant (F) is used, the amount thereof is usually 1 to 60 mass%, preferably 3 to 55 mass%, and more preferably 5 to 50 mass%, of the total nonvolatile components of the curable composition 5. Incidentally, when the colorant (F) has been dispersed using a dispersant or an alkali-soluble resin, the amount of the colorant (F) including the dispersant and alkali-soluble resin (excluding the volatile solvent) may be within the numerical range shown here.

[0164] (Other Optional Components) The curable composition 5 may contain optional components other than those described above. Examples of optional components include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion improvers, and antioxidants. Commercially available products can be used as these optional components. For example, the "KAYAMER" series manufactured by Nippon Kayaku Co., Ltd. can be used as an adhesion improver.

[0165] (Solvent) The curable composition 5 is usually a solution or dispersion of the above-mentioned various components in a solvent. The solvent usually contains an organic solvent.

[0166] Usable solvents are not particularly limited. Specific examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorine-containing solvents. These may be used alone or in combination of two or more.

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

[0168] Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

[0169] Examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

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

[0171] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone.

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

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

[0174] In addition, for the purpose of improving the coating property, turpentine-based petroleum naphtha solvents and paraffin-based solvents, which are high-boiling weak solvents, can be used.

[0175] Among them, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate Preferably, the solvent contains at least one selected from the group consisting of dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. Furthermore, the solvent preferably contains methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone.

[0176] When a solvent is used, only one solvent may be used, or two or more solvents may be used. When a solvent is used, the amount of solvent in the curable composition 5 is preferably used in an amount such that the total solids concentration becomes, for example, 5 to 85 mass %, specifically 10 to 60 mass %. The thickness of the film to be formed can be adjusted by adjusting the amount of solvent. Within the above range, it is easy to obtain a film with a thickness suitable for obtaining partition walls in organic EL elements.

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

[0178] [Oxygen-Containing Gas 7] The volume of oxygen-containing gas 7 is preferably adjusted appropriately, taking into consideration the need to bring a sufficient amount of oxygen into contact with the curable composition and the costs associated with storing and transporting the curable composition. The volume of oxygen-containing gas 7 is preferably 3 to 50% by volume of the volume of the container, more preferably 4 to 30% by volume, and even more preferably 8 to 30% by volume. The volume of oxygen-containing gas 7 may be 20% by volume or less, or 15% by volume or less.

[0179] The oxygen concentration of the oxygen-containing gas 7 is usually 1 to 100% by volume, preferably 5 to 50% by volume, and more preferably 20 to 25% by volume. An oxygen concentration of 1% by volume or more is believed to allow a sufficient amount of oxygen to come into contact with the curable composition, thereby sufficiently minimizing changes in the properties of the curable composition during storage. Furthermore, an oxygen concentration that is not too high is believed to be advantageous in terms of the balance of various performances, as it suppresses the excessive production of disulfide compounds.

[0180] The components other than oxygen in the oxygen-containing gas 7 are not particularly limited. The components other than oxygen usually include an inert component. Specifically, the oxygen-containing gas 7 preferably contains, in addition to oxygen gas, at least one selected from the group consisting of nitrogen gas and noble gases. Specific examples of noble gases include helium gas, neon gas, argon gas, and krypton gas. Of these, argon gas is preferred in terms of cost, ease of handling, and the like. The oxygen-containing gas 7 may or may not contain other gases such as carbon dioxide derived from the atmosphere.

[0181] It is preferable that the moisture content of the oxygen-containing gas 7 is small. This further suppresses changes in the properties of the curable composition. The moisture content of the oxygen-containing gas 7 is preferably 0.1% (1000 ppm) or less, and more preferably 0.01% (100 ppm) or less.

[0182] The pressure of the oxygen-containing gas 7 is not particularly limited. This pressure is preferably 0.5 to 1.5 atm, more preferably 0.8 to 1.2 atm, that is, near atmospheric pressure. A pressure near atmospheric pressure is preferable from the viewpoint of ease of packaging.

[0183] The net amount of oxygen in the oxygen-containing gas 7 is expressed as the volume of the oxygen-containing gas 7 multiplied by the oxygen concentration in the oxygen-containing gas 7. It is believed that by appropriately adjusting the amount of oxygen in the oxygen-containing gas 7, it is possible to sufficiently minimize changes in the properties of the curable composition during storage, while also improving other performances. Specifically, the value of {(volume of net oxygen in the oxygen-containing gas 7) / (volume of the curable composition 5)}×100(%) is preferably 0.05 to 10%, more preferably 0.1 to 8%, even more preferably 0.2 to 7%, particularly preferably 0.3 to 5%, and especially preferably 0.5 to 5%.

[0184] <Container containing curable composition: additional embodiment> Figure 2 is a diagram schematically illustrating a cross section of a container containing a curable composition, which is different from Figure 1. The container containing the curable composition specifically comprises: a container body 1; a lid 3 that can close the opening of the container body 1; an inner bag 11 contained inside the container body 1; a tube 13 provided inside the inner bag 11; a curable composition 5 contained inside the inner bag 11; and an oxygen-containing gas 7 that fills the part of the inner bag 11 that is not occupied by the curable composition 5.

[0185] The material of the inner bag 11 is not particularly limited. Any material may be used for the inner bag 11 as long as it is not substantially corroded by the curable composition 5. The inner bag 11 is preferably made of a resin. Examples of resins include polyolefins such as polyethylene and polypropylene, polycycloolefins, polystyrene, and polycarbonate. The inner bag 11 may also be made of a fluorine-based resin such as polytetrafluoroethylene. Using an inner bag 11 made of a fluorine-based resin can particularly reduce the elution of impurities from the inner bag 11 into the curable composition 5. When using the curable composition 5, the curable composition 5 can be removed by sucking it out of the tube 13. The material of the tube 13 is not particularly limited. The material of the tube 13 may be a metal such as iron or stainless steel, or a resin.

[0186] In the container shown in FIG. 2 , the container body 1 is not directly involved in storing the curable composition 5, but exists primarily to maintain the shape of the inner bag 11, keep it upright, and protect it. The inner bag 11 is essentially the container that contains the curable composition 5 and the oxygen-containing gas 7. Therefore, it is preferable to optimize the volume ratio of the oxygen-containing gas 7 and the filling rate of the curable composition 5 based on the internal volume of the inner bag 11 filled with the curable composition 5 and the oxygen-containing gas 7. Specifically, in the inner bag 11 filled with the curable composition 5 and the oxygen-containing gas 7, the volume of the oxygen-containing gas 7 is preferably 3 to 50 volume % of the internal volume of the inner bag 11, more preferably 4 to 30 volume %, and even more preferably 8 to 30 volume %. The volume of the oxygen-containing gas 7 may be 20 volume % or less, or 15 volume % or less.

[0187] The oxygen concentration of the oxygen-containing gas 7, the components other than oxygen in the oxygen-containing gas 7, the moisture content of the oxygen-containing gas 7, the pressure of the oxygen-containing gas 7, the net amount of oxygen in the oxygen-containing gas 7, and the like can be the same as those of the container containing the curable composition described in Fig. 1. Furthermore, the curable composition 5 in Fig. 2 can be the same as the curable composition 5 described in Fig. 1. For other matters not described in Fig. 2, the matters described in Fig. 1 can be appropriately referenced.

[0188] Incidentally, a container having an inner bag 11 as shown in Fig. 2 is usually used without putting gas into the inner bag 11. In other words, a container having an inner bag 11 as shown in Fig. 2 has conventionally been used to store a curable composition without contacting it with gases such as air. In other words, the embodiment shown in Fig. 2 intentionally brings a gas (oxygen-containing gas) into contact with the curable composition using a container that has conventionally been used to prevent the curable composition from contacting with gas. Such an embodiment is based on an original idea of ​​the present inventors.

[0189] <Method for producing curable composition> The above describes an embodiment of the technical idea conceived by the present inventors from the perspective of a "container containing a curable composition." From a different perspective, the technical idea conceived by the present inventors can also be expressed as a method for producing a curable composition.

[0190] Specifically, the technical idea conceived by the present inventors can also be expressed as a method for producing a curable composition as follows.

[0191] A method for producing a curable composition, comprising: a preparation step of mixing a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator to prepare a mixture; and an oxygen contact step of contacting the mixture with an oxygen-containing gas.

[0192] Specific examples and amounts of the one or more thiol compounds selected from the group consisting of a compound having an ethylenic carbon-carbon double bond, a thiol, and a thiol precursor, and the radical initiator are as described in the section [Curable composition 5] in <Container containing curable composition>. The same applies to components that can be optionally contained in the mixture or curable composition and their amounts.

[0193] The oxygen contact step can usually be carried out by placing the mixture together with an oxygen-containing gas in a hermetically sealed container, sealing it, and leaving it to stand for a while. Specific embodiments of the hermetically sealed container are as described in [Container body 1 and lid 3] in <Container containing curable composition>. Also included are the containers described in <Container containing curable composition: additional embodiment>. Specific embodiments of the oxygen-containing gas are as described in the [Oxygen-containing gas 7] section in <Container containing curable composition>.

[0194] The oxygen contact step is usually carried out for 1 to 180 days, preferably 7 to 120 days, at a temperature of usually 3 to 35°C, preferably 5 to 25°C.

[0195] Between the preparation step and the oxygen contact step, a degassing step may be performed to remove dissolved gases from the mixture. Degassing can be performed, for example, by treating the mixture in an environment with a pressure lower than 1 atm. By performing the degassing step to reduce the amount of dissolved gases in the curable composition, it may be possible to suppress the generation of bubbles, for example, when the curable composition is applied to a substrate to form a film. By reducing the amount of oxygen in the curable composition through the degassing step and then deliberately contacting the curable composition with oxygen in the subsequent oxygen contact step, it is possible to produce a curable composition with minimal changes in properties due to storage. Incidentally, as long as the pressure of the oxygen-containing gas contacted with the curable composition in the oxygen contact step is not too high (for example, 1.5 atm or less), the effect of suppressing bubble generation by degassing can be sufficiently obtained.

[0196] <Method for Producing Cured Film, Pattern, Light-Emitting Device, and Display Device> A cured film can be produced by carrying out a film-forming step of applying the curable composition in the container containing the curable composition (for example, curable composition 5 in Fig. 1 or 2) onto a substrate to form a film, and a heating step of heating and curing the film.

[0197] In particular, when the curable composition is photosensitive, a cured film, specifically a pattern composed of a cured product, can be produced by carrying out the following steps: a film-forming step of applying the curable composition in the container containing the curable composition onto a substrate to form a film; an exposure step of patternwise exposing the film; a development step of developing the exposed film; and a heating step of heating and curing the developed film.

[0198] A curable composition containing the components described above is preferably used to form partition walls in a light-emitting device, as described in, for example, Patent Document 1. That is, in the series of steps described above, by appropriately designing the "pattern" of the patterned exposure in the exposure step, it is possible to produce partition walls of a desired size and shape (specifically, partition walls having "recesses" for dropping ink) made of a cured product. Then, it is possible to produce a light-emitting device that includes such partition walls and a light-emitting layer or a wavelength conversion layer disposed in the region defined by the partition walls (corresponding to the recesses). Furthermore, it is possible to produce a display device using the light-emitting device.

[0199] Hereinafter, a method for producing a pattern, specifically a pattern used as a partition wall in a light-emitting device, using a photosensitive curable composition will be described.

[0200] [Film Forming Step] In the film forming step, a photosensitive curable composition is applied onto a substrate to form a film.

[0201] The type of substrate is not particularly limited. The substrate may be appropriately selected depending on the product to be manufactured. Examples of substrate types include silicon wafers, SiN substrates, metal substrates, glass substrates, substrates with ITO films, substrates containing metal oxides, and organic resin substrates (e.g., polyimide, polycarbonate, polyester). A layer of some kind may be formed on at least one surface of the substrate. For example, when manufacturing a light-emitting device, a first light-emitting layer may be disposed on at least one surface of the substrate. Examples of the first light-emitting layer include a layer formed from an organic electroluminescent (EL) light-emitting material, an LED light-emitting material such as a mini-LED, μ-LED, or nano-LED, or a quantum dot light-emitting material. The first light-emitting layer may be a monochromatic layer or a multi-color layer, but a monochromatic layer is preferred. Furthermore, the first light-emitting layer is preferably a monochromatic blue light-emitting layer. When a first light-emitting layer is disposed on at least one surface of the substrate, an organic or inorganic film may be disposed between the substrate and the first light-emitting layer. For example, an anti-reflective film, a multilayer resist underlayer, or a barrier layer may be provided. In addition, a driving circuit, an electrode, a planarization layer, etc. may be formed between the substrate and the first light-emitting layer. In addition, a wavelength conversion layer may be provided instead of the first light-emitting layer. Just to be clear, the substrate may not have a layer such as the first light-emitting layer formed on its surface.

[0202] The method for applying the curable composition is not particularly limited. Known methods such as spin coating, bar coating, and curtain coating can be used. In some cases, inkjet printing can also be applied. When a solvent-containing curable composition is used, it is preferable to dry the solvent by heating after applying the photosensitive curable composition. The heating temperature can be, for example, 50 to 150°C, preferably 50 to 100°C, more preferably 60 to 90°C, even more preferably 70 to 90°C, and particularly preferably 80 to 90°C. The heating time can be 60 to 200 seconds. The film thickness (dry thickness) of the film is usually 0.5 to 20 μm, preferably 1 to 15 μm.

[0203] [Exposure Step] In the exposure step, the film obtained in the film-forming step is exposed to a pattern. Specifically, light generated from a light source of an exposure device is irradiated onto the film through a photomask. The light can be ultraviolet light, gamma rays, X-rays, etc. Due to the availability of light sources, ultraviolet light (particularly g-rays, i-rays, etc.) is mainly used as the light. The exposure dose is not particularly limited, but is usually 1 to 200 mJ / cm. ２ , preferably 10 to 100 mJ / cm ２ After the exposure and before the development step described below, a heat treatment may or may not be carried out.

[0204] In the development step, the film after the exposure step is typically developed using a developer, which usually dissolves the unexposed areas in the film, thereby obtaining a pattern (partition walls).

[0205] An alkaline aqueous solution is preferably used as the developer. Specifically, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, etc. can be used. As the developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferred in view of its good developability and long track record of use in the field of photosensitive compositions. The concentration of the TMAH aqueous solution is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass. Incidentally, a developer containing an organic solvent as its main component may be used in some cases.

[0206] As the developing method, known methods can be used, such as a dipping method, a puddle method, a spray method, etc. The developing time (the time during which the developer is in contact with the film) is preferably from 10 seconds to 3 minutes, and more preferably from 30 seconds to 2 minutes.

[0207] After the development treatment, if necessary, a step of washing the pattern with deionized water etc. The washing time is preferably from 10 seconds to 3 minutes, more preferably from 30 seconds to 2 minutes.

[0208] [Heating Step] In the heating step, the developed film is heated. This allows the remaining reactive groups in the pattern obtained in the development step to react as much as possible, thereby hardening the film. In the heating step, the developed film is heated, for example, at 50 to 250°C, preferably 50 to 230°C, more preferably 60 to 220°C, and even more preferably 70 to 200°C. By not raising the heating temperature too much, it is easy to suppress alteration and deterioration of the dye and other materials in the light-emitting element. The heating time is, for example, 10 minutes to 3 hours, preferably 15 minutes to 1 hour.

[0209] [Optional Steps After Heating Step] The cured film obtained in the heating step may be subjected to UV ozone treatment or oxygen plasma treatment, which can remove organic matter remaining in the recesses of the pattern (cured film) and reduce uneven wetting of the dropped ink during the ink dropping process described below.

[0210] To obtain a light-emitting element, a second light-emitting layer formation step is preferably performed, in which a second light-emitting layer that emits light using light from the first light-emitting layer as excitation light is formed in the recesses of the pattern (cured film), i.e., in the areas partitioned by the partition walls. The second light-emitting layer preferably contains a conventionally known material, such as a quantum dot light-emitting material. As described in the Background Art section, the second light-emitting layer can be formed, for example, by depositing ink droplets into the recesses of the pattern (cured film) using an inkjet method and then drying and / or solidifying the ink. In other words, a light-emitting element may be obtained by depositing ink for forming the second light-emitting layer droplets into the recesses of the pattern (cured film) using an inkjet method.

[0211] Alternatively, in order to obtain a light-emitting element that emits RGB light, ink containing a red, green, or blue dye (typically, a liquid in which a pigment is dispersed) may be dropped into the recesses of the pattern (cured film), i.e., the areas defined by the partition walls, and then the ink may be dried and / or solidified.

[0212] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0213] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, it should be noted that the present invention is not limited to the Examples.

[0214] First, various measurement methods will be described. [Mole ratio of each structural unit in polymer] １ H-NMR, １９ F-NMR or １３ The weight average molecular weight Mw and molecular weight dispersity (ratio of number average molecular weight Mn to weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, Model HLC-8320GPC) with one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) connected in series, using polystyrene as a standard substance and tetrahydrofuran (THF) as a developing solvent. A refractive index difference detector was used as the detector.

[0215] <Preparation (Synthesis or Preparation) of Raw Materials> [Synthesis of Fluorine-Containing Resin 1] Into a 300 mL glass flask equipped with a stirrer, 2.9 parts by mass of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd.; hereinafter referred to as BTFBE), 2.9 parts by mass of 4-acetoxystyrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St), 12.5 parts by mass of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 6.0 parts by mass of glycerin monomethacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as Gly-MA), and 125 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed at room temperature (about 20°C). Thereafter, 2.3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was further added to the flask, and the mixture was degassed with stirring. Thereafter, the atmosphere in the flask was purged with nitrogen gas, and the internal temperature was raised to 79°C, followed by reaction overnight. In this manner, a precursor solution of fluororesin 1 was obtained.

[0216] The structure of the precursor of fluororesin 1 is as shown below. The composition ratio of the structural units of the precursor of fluororesin 1, in molar ratio, was (structural units derived from BTFBE):(structural units derived from p-AcO-St):(structural units derived from MA-C6F):(structural units derived from Gly-MA)=15:18:29:38.

[0217]

[0218] After completion of the reaction, the atmosphere in the flask was replaced with dry air, and the reaction solution was cooled to an internal temperature of 60°C. After cooling, 0.01 parts by mass of dibutylhydroxytoluene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 11.4 parts by mass of 2-isocyanatoethyl acrylate (a product of Showa Denko K.K., product name: Karenz AOI) were added to the flask and stirred for 4 hours. The stirred solution was then cooled to room temperature (20°C). In this way, a solution of fluororesin 1 was obtained. Based on the results of GPC measurement, the Mw of fluororesin 1 was 13,300, and the Mw / Mn was 1.7.

[0219] [Preparation of Black Pigment Dispersion 1] The pigment, dispersant, alkali-soluble resin, and solvent shown in the table below were mixed in the mass ratio shown in the table below to prepare a mixture. This mixture was dispersed in a bead mill at 25°C for 12 hours using 0.5 mmφ zirconia beads. After the dispersion process was completed, the beads were removed by filtration. In this way, Black Pigment Dispersion 1 was prepared.

[0220]

[0221] [Preparation of Blue Pigment Dispersion] The pigment, dispersant, alkali-soluble resin, and solvent shown in the table below were mixed in the mass ratio shown in the table below to prepare a mixture. This mixture was dispersed in a bead mill at 25°C for 12 hours using 0.5 mmφ zirconia beads. After dispersion was completed, the beads were removed by filtration. In this way, a blue pigment dispersion was prepared.

[0222]

[0223] <Preparation of curable composition and packaging> First, the components used to prepare the curable composition will be shown. [Compounds having an ethylenic carbon-carbon double bond] Ethylenically unsaturated compound 1: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. [Thio-based compounds] Thiol compound 1: "Karenz-MTPE1" manufactured by Showa Denko K.K. Thiol compound 2: "DPMP" manufactured by SC Organic Chemical Industry Co., Ltd. [Radical initiators] Photoradical initiator 1: "Irgacure OXE-01" (oxime ester type) manufactured by BASF [Fluorine-containing resins] Fluorine-containing resin 1: Fluorine-containing resin synthesized as described above [Alkali-soluble resins] Alkali-soluble resin 1: "ZAR-2050H" manufactured by Nippon Kayaku Co., Ltd. (special BIS-A type epoxy acrylate, containing a structural unit represented by the above general formula (1), containing no fluorine atoms) [Color pigment dispersions] Black pigment dispersion 1: Black pigment dispersion prepared as described above White pigment dispersion ("NX-501" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (titanium oxide pigment, rutile structure, pigment content: 73% by mass, particle diameter: D50 is 270 nm) Blue pigment dispersion: blue pigment dispersion prepared as above [Additives] Additive 1: adhesion improver "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd.

[0224] The following oxygen-containing gases were prepared to be sealed in a container together with the curable composition: [Oxygen-containing gases or gases for comparative examples] Air: air (oxygen content is usually about 21% by volume) 7% O ２ : A mixed gas of 7% oxygen and 93% nitrogen by volume N ２ : 100% nitrogen Ar: 100% argon

[0225] Each component listed in the table below and PGMEA as a solvent were uniformly stirred and mixed to prepare a photosensitive curable composition. The amount of PGMEA was adjusted to a nonvolatile component concentration of 50% by mass. The prepared curable composition was placed in a 200 mL polyethylene light-shielding container manufactured by Sanplatec Co., Ltd. The amount of curable composition was adjusted so that the container was not filled to capacity with the curable composition, but rather a gap of the volume percentage indicated in the "Oxygen-Containing Gas Percentage (Volume %) in the Container" table was left. For example, in Example 1, 100% by volume - 10% by volume = 90% by volume of the curable composition was placed in the container relative to the total volume of the container. The air in the light-shielding container was then replaced with the oxygen-containing gas. The lid was then tightly closed to create a container containing the curable composition. This container was then stored.

[0226] <Evaluation> [Formation of Partition Ribs for Evaluation] Partition ribs (patterns) were formed on a substrate using the following procedure. (1) A 10 cm square ITO substrate was washed with ultrapure water and then with acetone. Then, the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Sources Co., Ltd., model number PL17-110). (2) After the UV ozone treatment, a curable composition was applied to the substrate using a spin coater at a rotation speed of 300 rpm. The substrate was then heated on a hot plate at 80°C for 150 seconds. A resin film was thus obtained. (3) Using a mask aligner (manufactured by SUSS MicroTec Co., Ltd.), the obtained resin film was irradiated with i-line light (wavelength 365 nm) through a mask with a line:space ratio of 10 μm:10 μm. (4) Spray development was performed for 40 seconds using a 0.04% by mass potassium hydroxide aqueous solution. After development, the substrate was rinsed with pure water for 10 seconds. The remaining developer and / or rinse solution was then washed away with N ２ The film was removed by blowing. (5) The substrate was heated on a hot plate at 200° C. for 60 minutes.

[0227] [Evaluation of Sensitivity and Resolution] The exposure dose in (3) of [Formation of barrier ribs for evaluation] above was changed to determine the exposure dose that allows a pattern with a line:space=10 μm:10 μm to be formed on a substrate using a mask pattern with a line:space=10 μm:10 μm, that is, the optimal exposure dose E at which a pattern with the same line width as the mask pattern is resolved. ｏｐ (mJ / cm ２ ) was obtained. ｏｐ was used as an index of sensitivity.

[0228] In addition, the optimum exposure amount E ｏｐ The barrier rib pattern obtained in step 1 was observed under a microscope, and the resolution was evaluated according to the following criteria: - No residue in the openings in the barrier ribs, and no line edge roughness was observed: Excellent - Slight residue in the openings or line edge roughness was observed: Good - At least one of residue in the openings and line edge roughness was noticeable: Unacceptable

[0229] [Changes in Properties Due to Storage: Viscosity Changes] The viscosity of the curable composition immediately after preparation and before packaging was measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd., model DV2T) at a sample temperature of 25°C and a spindle rotation speed of 15 rpm. The spindle used was a Spindle ULA (manufactured by AMETEC). The measurement was performed six times, and the average of the six values ​​obtained was taken as the viscosity (before storage) η ０ In addition, the viscosity of the curable composition after storing it at 40°C for 7 days after packaging was measured six times in the same manner, and the average value was calculated. The average value was then used as the viscosity (after storage) η １ Then, the formula: (|η １ -η ０ | / η ０ ) × 100 (%), the viscosity change rate before and after storage was calculated. The evaluation criteria were as follows: Viscosity change rate of 5% or less: Excellent Viscosity change rate of more than 5% but not more than 10%: Good Viscosity change rate of more than 10% but not more than 15%: Acceptable Viscosity change rate of more than 15% or solidification that made measurement impossible: Unacceptable

[0230] [Storage stability: resolution] Using a curable composition that had been placed in a container and then allowed to stand at 40°C for 7 days, partition walls (patterns) were formed in the same manner as in [Formation of partition walls for evaluation]. The partition walls thus obtained were compared with partition walls formed using the curable composition before aging. Evaluation was then based on the following criteria. Excellent: The appearance was equivalent to that of partition walls formed using the curable composition before storage. Good: Compared to partition walls formed using the curable composition before storage, foreign matter and / or residue was observed in a part of the opening. Fair: Compared to partition walls formed using the curable composition before storage, foreign matter and / or residue was observed in the entire opening. Poor: The unexposed areas did not dissolve even after development, and a pattern could not be formed.

[0231] The information on the components of the curable composition and the evaluation results are summarized in the table below. In the table, the ratio of the amounts of components used in the preparation of the composition in the form of a solution or dispersion is also shown converted to the amount of nonvolatile components.

[0232]

[0233]

[0234] In the Examples, the sensitivity and resolution were good. Furthermore, the viscosity change was small when the ink was bottled and left to stand at 40°C for 7 days. A detailed analysis of the Examples reveals that the presence of a certain amount of oxygen in the container, compared with Examples 1 to 6 and 10 to 14 and Examples 7 to 9, reduces the viscosity change before and after storage.

[0235] In contrast to the Examples, in Comparative Examples 1 to 9 in which the enclosed gas did not contain oxygen, the properties of the curable compositions changed significantly after being packed into a container and left standing at 40°C for 7 days.

[0236] <Reference: Confirmation of Formation of Disulfide Compounds> In Example 1, the curable composition was packed into a container and allowed to stand at 40°C for 7 days, and then the curable composition in the container was subjected to GPC measurement. As a result, a peak thought to be a disulfide compound formed by oxidation of thiol compound 1 was observed. In contrast, a similar GPC measurement was also performed in Comparative Example 1, but no peak thought to be a disulfide compound was observed. These results support the presumed mechanism that a disulfide compound formed by reaction of oxygen in an oxygen-containing gas with a thiol compound in the curable composition suppresses deterioration of the curable composition.

[0237] This application claims priority based on Japanese Patent Application No. 2023-111649, filed on July 6, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0238] REFERENCE SIGNS LIST 1 Container body 3 Lid 5 Curable composition 7 Oxygen-containing gas 11 Inner bag 13 Tube

Claims

1. A container containing a curable composition, the container comprising: a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator; and an oxygen-containing gas, the container being hermetically sealed with the curable composition.

2. A container containing a curable composition according to claim 1, wherein the volume of the oxygen-containing gas is 3 to 50 volume % of the volume of the container.

3. A container containing a curable composition according to claim 1 or 2, wherein the oxygen-containing gas has an oxygen concentration of 1 to 100% by volume.

4. A container containing a curable composition according to claim 1 or 2, wherein the oxygen-containing gas has an oxygen concentration of 20 to 25% by volume.

5. A container containing a curable composition according to claim 1 or 2, wherein the pressure of the oxygen-containing gas is 0.5 to 1.5 atm.

6. A container containing a curable composition according to claim 1 or 2, wherein the oxygen-containing gas contains at least one selected from the group consisting of nitrogen gas and noble gases.

7. A container containing a curable composition according to claim 1 or 2, wherein the surface of the container having the sealability that comes into contact with the curable composition is made of a resin.

8. A container containing a curable composition according to claim 1 or 2, wherein the container having a sealability is provided with a light-shielding property.

9. A container containing a curable composition according to claim 1 or 2, wherein the radical initiator comprises a photoradical initiator.

10. A container containing a curable composition according to claim 1 or 2, wherein the curable composition contains a disulfide compound.

11. A container containing the curable composition according to claim 1 or 2, wherein the curable composition further contains an alkali-soluble resin.

12. A container containing the curable composition according to claim 1 or 2, wherein the curable composition further contains a fluorine-containing resin.

13. A container containing the curable composition according to claim 1 or 2, wherein the curable composition further comprises a colorant.

14. A container containing a curable composition according to claim 1 or 2, wherein the viscosity of the curable composition in the container is measured using a B-type viscometer and is η ０ The viscosity of the curable composition in the container containing the curable composition, measured using a B-type viscometer after storing the container containing the curable composition at 40° C. for 7 days, is defined as η １ Then, (|η １ -η ０ | / η ０ A container containing a curable composition, wherein the viscosity change rate defined as (a) x 100(%) is 15% or less.

15. A container containing a curable composition according to claim 1 or 2, wherein the curable composition in the container is used to form a partition wall in a light-emitting device.

16. A method for producing a cured film, comprising: a film-forming step of applying the curable composition in a container containing the curable composition according to claim 1 or 2 onto a substrate to form a film; and a heating step of heating and curing the film.

17. A pattern composed of a cured product of the curable composition in a container containing the curable composition according to claim 1 or 2.

18. The pattern according to claim 17, which is used as a partition in a light-emitting element.

19. A light-emitting element comprising the pattern according to claim 17 and a light-emitting layer or a wavelength conversion layer disposed in an area defined by said pattern.

20. A display device comprising the light-emitting element according to claim 19.

21. A method for producing a curable composition, comprising: a preparation step of mixing a compound having an ethylenic carbon-carbon double bond, one or more thiol compounds selected from the group consisting of thiols and thiol precursors, and a radical initiator to prepare a mixture; and an oxygen contact step of contacting the mixture with an oxygen-containing gas.

22. A method for producing a curable composition according to claim 21, wherein the oxygen contact step is carried out for 1 to 180 days.

23. A method for producing a curable composition according to claim 21 or 22, wherein the oxygen contact step is carried out at 3 to 35°C.

24. A method for producing a curable composition according to claim 21 or 22, comprising a degassing step of degassing dissolved gas in the mixture between the preparation step and the oxygen contact step.