Photosensitive resin composition and method for producing fluorine-containing resin cured product

Abstract

To provide a photosensitive resin composition having good water-repellent property.SOLUTION: A photosensitive resin composition contains at least a fluorine-containing resin having a crosslinked site, a solvent, and a photopolymerization initiator, wherein the fluorine-containing resin includes a repeating unit composed of hydrocarbon having a fluorine atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition and a method for producing a cured fluorine-containing resin product. [Background technology]

[0002] Inkjet printing is known as a method for forming organic layers with functions such as light emission when manufacturing display elements such as organic electroluminescence (EL) displays, micro LED displays, and quantum dot displays. There are several inkjet printing methods, including one in which ink is dropped from a nozzle onto recesses of a patterned film with irregularities formed on a substrate and then solidified, and another in which ink droplets are dropped onto a patterned film previously formed on a substrate, with lyophilic areas that are ink-wettable and lyophobic areas that repel ink, and the ink adheres only to the lyophilic areas.

[0003] In particular, in the former method of solidifying ink dropped from a nozzle into the recesses of a patterned film, two main methods can be used to create such a patterned film with irregularities. One is photolithography, in which the surface of a photosensitive resist film applied to a substrate is exposed to light in a patterned manner to form exposed and unexposed areas, and one of these areas is then dissolved and removed using a developer. The other is imprinting, which uses printing technology. After forming a patterned film with irregularities, the entire substrate is typically subjected to UV ozone treatment or oxygen plasma treatment. This UV ozone treatment or oxygen plasma treatment can remove residual organic matter, especially in the recesses of the patterned film, reducing uneven wetting of the dropped ink and preventing display device defects.

[0004] The convex portions of the patterned film with the resulting unevenness are called banks (partition walls), and they act as barriers to prevent the inks from mixing when dropped into the concave portions of the patterned film. To enhance this barrier effect, the concave portions of the patterned film must expose the substrate surface, and the substrate surface must be lyophilic to the ink, while the top surface of the bank must be liquid-repellent to the ink.

[0005] Patent Document 1 discloses a photosensitive resin composition containing a vinyl polymer having a side chain with an epoxy group. Patent Document 2 discloses a fluorine-containing polymer that can be thermally cured at low temperatures (room temperature to 150° C.) and contains repeating units having fluorine atoms in the main chain. Furthermore, compositions containing a fluorine-based polymer having an acrylic moiety in the main chain as a liquid repellent for ink are known as compositions for forming banks for organic EL devices (for example, Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-142753 [Patent Document 2] International Publication No. 2018 / 43165 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-172742 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-108499 Summary of the Invention [Problem to be solved by the invention]

[0007] However, when a cured resin product is produced using the resin compositions described in Patent Documents 1 and 2, the cured resin product does not have sufficient liquid repellency, making it difficult to use in applications where liquid repellency is required.

[0008] An object of the present disclosure is to provide a photosensitive resin composition having good liquid repellency. [Means for solving the problem]

[0009] The present inventors have conducted extensive research in view of the above problems, and as a result have found that the above problems can be solved by a photosensitive resin composition comprising at least a fluorine-containing resin having a cross-linking moiety, a solvent, and a photopolymerization initiator, wherein the fluorine-containing resin contains a repeating unit composed of a hydrocarbon having a fluorine atom, and have arrived at the present disclosure.

[0010] A cured fluorine-containing resin obtained by curing the photosensitive resin composition of the present disclosure also has excellent liquid repellency. Therefore, when the photosensitive resin composition of the present disclosure is used to form a bank for an organic electroluminescence display, a micro LED display, a quantum dot display, or the like, the bank exhibits excellent ink liquid repellency.

[0011] That is, the present disclosure is as follows.

[0012] [Invention 1] The composition contains at least a fluorine-containing resin having a crosslinking site, a solvent, and a photopolymerization initiator, A photosensitive resin composition, wherein the fluorine-containing resin contains a repeating unit consisting of a hydrocarbon having a fluorine atom.

[0013] [Invention 2] The photosensitive resin composition according to Invention 1, wherein the repeating unit comprising a hydrocarbon having a fluorine atom has a structure represented by the following formula (1-1):

[0014] [ka] (In formula (1-1), each Rf independently represents 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. R 1-2 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.

[0015] [Invention 3] The photosensitive resin composition according to invention 1 or 2, wherein the repeating unit comprising a hydrocarbon having a fluorine atom has a structure represented by the following formula (1-2):

[0016] [ka] (In formula (1-2), each Rf independently represents 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. R 1-1 represents a hydrogen atom, a fluorine atom, or a methyl group. 1-2 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.

[0017] [Invention 4] 4. The photosensitive resin composition according to claim 2, wherein Rf in the formula (1-1) or (1-2) is 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.

[0018] [Invention 5] 5. The photosensitive resin composition according to any one of Inventions 1 to 4, wherein the fluorine content of the fluororesin is 20 to 50% by mass.

[0019] [Invention 6] 6. The photosensitive resin composition according to any one of inventions 1 to 5, further comprising a crosslinking agent.

[0020] [Invention 7] 7. The photosensitive resin composition according to any one of Inventions 1 to 6, further comprising an alkali-soluble resin.

[0021] [Invention 8] 8. The photosensitive resin composition according to any one of claims 1 to 7, which is cured at a temperature of 140°C or less.

[0022] [Invention 9] A method for producing a cured fluorine-containing resin product, comprising: 9. A method for producing a cured fluorine-containing resin product, comprising a baking step of curing the photosensitive resin composition according to any one of Inventions 1 to 8 by baking at a temperature of 140° C. or lower.

[0023] [Invention 10] 10. The method for producing a cured fluorine-containing resin product according to invention 9, wherein the photosensitive resin composition is baked at 60 to 130°C in the baking step.

[0024] [Invention 11] 11. The method for producing a cured fluorine-containing resin product according to Invention 9 or 10, further comprising, before the baking step, an exposure step of exposing the photosensitive resin composition to high-energy rays.

[0025] [Invention 12] 12. The method for producing a cured fluorine-containing resin product according to claim 11, wherein the high-energy radiation is at least one type selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0026] [Invention 13] A method for producing a cured fluorine-containing resin product, comprising: a film-forming step of applying the photosensitive resin composition according to any one of Inventions 1 to 8 onto a substrate and then heating the composition to form a fluorine-containing resin film; an exposure step of exposing the fluorine-containing resin film to high-energy rays; a developing step of developing the fluorine-containing resin film after the exposure step with an alkaline aqueous solution to form a fluorine-containing resin patterned film; a baking step of baking the fluorine-containing resin patterned film at a temperature of 140°C or less to cure the film, after the developing step, to form a fluorine-containing resin cured product.

[0027] [Invention 14] A fluorine-containing resin containing both a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2).

[0028] [ka] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 , R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (2-2), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3.

[0029] [Invention 15] R 2-3 , R 2-4are each independently 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.

[0030] [Invention 16] 16. The fluorine-containing resin according to invention 14 or 15, further comprising a repeating unit represented by formula (2-3):

[0031] [ka] [In formula (2-3), R 2-7 represents a hydrogen atom or a methyl group. R 2-8 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, and the fluorine content in the repeating unit is 30% by mass or more.]

[0032] [Invention 17] 17. The fluorine-containing resin according to any one of inventions 14 to 16, further comprising a repeating unit represented by formula (2-4).

[0033] [ka] [In formula (2-4), R 2-9 represents a hydrogen atom or a methyl group. B 2 are each independently a hydroxyl group, a carboxyl group, -C(=O)-OR 2-10 (R 2-10 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, and R 2-10 The fluorine content in the alkyl group is 30 mass % or more.2-11 (R 2-11 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. m represents an integer of 0 to 3.

[0034] [Invention 18] A photosensitive resin composition comprising at least the fluorine-containing resin according to any one of inventions 14 to 17, a solvent, and a photopolymerization initiator.

[0035] [Invention 19] The solvent may be 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 mono 19. The photosensitive resin composition according to Invention 18, wherein the hydroxybenzoate is at least one selected from the group consisting of methyl 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.

[0036] [Invention 20] 20. The photosensitive resin composition according to claim 18 or 19, further comprising a crosslinking agent and an alkali-soluble resin.

[0037] [Invention 21] A fluorine-containing resin film containing both a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2A).

[0038] [ka] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 , R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (2-2A), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3.

[0039] [Invention 22] A bank containing both a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2A).

[0040] [ka] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 、 R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (2-2A), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3.

[0041] [Invention 23] A display element comprising the bank according to invention 22.

[0042] [Invention 24] A fluorine-containing resin containing both a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2).

[0043] [ka] [In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 3-2 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. R 3-3 , R 3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (3-2), R 3-5 , R 3-6 each independently represents a hydrogen atom or a methyl group. W 3 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 3-1 , A 3-2 represents a divalent linking group, each independently representing 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. Y 3-1 , Y 3-2 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1.

[0044] [Invention 25] R 3-3 , R 3-4 are each independently 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.

[0045] [Invention 26] 26. The fluorine-containing resin according to invention 24 or 25, further comprising a repeating unit represented by formula (3-3):

[0046] [ka] [In formula (3-3), R 3-7 represents a hydrogen atom or a methyl group. R 3-8 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, and the fluorine content in the repeating unit is 30% by mass or more.]

[0047] [Invention 27] 27. The fluorine-containing resin according to any one of Inventions 24 to 26, further comprising a repeating unit represented by formula (3-4).

[0048] [ka] [In formula (3-4), R 3-5 , Y 3-1 , A 3-1 and r is R in the formula (3-2). 3-5 , Y 3-1 , A 3-1 and r, respectively. E 3-1represents a hydroxyl group, a carboxyl group, or an oxirane group. s represents 0 or 1.]

[0049] [Invention 28] 28. The fluorine-containing resin according to any one of Inventions 24 to 27, further comprising a repeating unit represented by formula (3-6).

[0050] [ka] [In formula (3-6), R 3-6 , Y 3-1 is R in the formula (3-2). 3-6 , Y 3-1 are equivalent to the above.]

[0051] [Invention 29] 29. The fluorine-containing resin according to any one of Inventions 24 to 28, further comprising a repeating unit represented by formula (3-5).

[0052] [ka] [In formula (3-5), R 3-9 represents a hydrogen atom or a methyl group. B 3 are each independently a hydroxyl group, a carboxyl group, -C(=O)-OR 3-10 (R 3-10 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, and R 3-10 The fluorine content in the alkyl group is 30 mass % or more. 3-11 (R 3-11 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. m represents an integer of 0 to 3.

[0053] [Invention 30] 30. A photosensitive resin composition comprising at least the fluorine-containing resin according to any one of inventions 24 to 29, a solvent, and a photopolymerization initiator.

[0054] [Invention 31] The solvent may be 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 mono 31. The photosensitive resin composition according to Invention 30, wherein the hydroxybenzoate is at least one selected from the group consisting of methyl 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.

[0055] [Invention 32] 32. The photosensitive resin composition according to claim 30, further comprising a crosslinking agent and an alkali-soluble resin.

[0056] [Invention 33] A fluorine-containing resin film containing both a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2A).

[0057] [ka] [In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 3-2 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. R 3-3 , R 3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (3-2A), R 3-5 , R 3-6 each independently represents a hydrogen atom or a methyl group. W 3 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 3-1 , A 3-2 represents a divalent linking group, each independently representing 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. Y 3-1 , Y 3-2 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1.

[0058] [Invention 34] A bank containing both a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2A).

[0059] [ka] [In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 3-2 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. R 3-3 , R 3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (3-2A), R 3-5 , R 3-6 each independently represents a hydrogen atom or a methyl group. W 3 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 3-1 , A 3-2 represents a divalent linking group, each independently representing 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. Y 3-1 , Y 3-2 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1.

[0060] [Invention 35] A display element comprising the bank according to invention 34. [Effects of the Invention]

[0061] According to the present disclosure, a photosensitive resin composition having good liquid repellency can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0062] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0063] In the "Form for Carrying Out the Invention" section of this specification, items indicated by "[" and "]", "<" and ">" are merely symbols and have no meaning in themselves. In this specification, the terms "polymer" and "resin" are synonymous and mean a polymeric compound unless otherwise noted.

[0064] In this specification, the terms "bank" and "partition wall" are synonymous and mean the convex portions of a pattern film having concaves and convexes in an inkjet method, unless otherwise noted.

[0065] In this specification, the "upper surface of the bank" refers to the upper surface of the convex portion of the pattern film having concaves and convexes in the inkjet method (the surface that is far from the substrate surface in the vertical direction), and does not include the wall surface of the convex portion.

[0066] In this specification, "resistance to UV ozone treatment or oxygen plasma treatment" means that the amount of film loss before and after UV ozone treatment or oxygen plasma treatment is small, that is, the change in film thickness is small.

[0067] (First embodiment) The photosensitive resin composition according to the first embodiment of the present disclosure is characterized in that it contains at least a fluorine-containing resin having a cross-linking moiety, a solvent, and a photopolymerization initiator, and the fluorine-containing resin contains a repeating unit composed of a hydrocarbon having a fluorine atom.

[0068] Such a photosensitive resin composition according to the first embodiment of the present disclosure can be cured at low temperatures, and a cured product of the photosensitive resin composition according to the first embodiment of the present disclosure will have good liquid repellency.

[0069] The photosensitive resin composition according to the first embodiment of the present disclosure can be cured at low temperatures. Therefore, when the photosensitive resin composition according to the first embodiment of the present disclosure is used to form a bank for an organic electroluminescence display, a micro LED display, a quantum dot display, or the like, the bank can be formed without causing significant thermal damage to the light-emitting layer. The photosensitive resin composition according to the first embodiment of the present disclosure is preferably cured at a temperature of 140°C or less, and more preferably at a temperature of 60 to 130°C or less.

[0070] Furthermore, a fluorine-containing resin cured product obtained by curing the photosensitive resin composition according to the first embodiment of the present disclosure also has excellent liquid repellency. Therefore, when the photosensitive resin composition according to the first embodiment of the present disclosure is used to form a bank for an organic electroluminescence display, a micro LED display, a quantum dot display, or the like, the bank exhibits excellent ink repellency.

[0071] Hereinafter, each component of the photosensitive resin composition according to the first embodiment of the present disclosure will be described.

[0072] <Fluorine-containing resin> In the photosensitive resin composition according to the first embodiment of the present disclosure, as the fluorine-containing resin, the repeating unit composed of a hydrocarbon having a fluorine atom preferably has a structure represented by the following chemical formula (1-1), and more preferably has a structure represented by the following formula (1-2).

[0073] [ka] (In formula (1-1), each Rf independently represents 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. R 1-2represents 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.

[0074] [ka] (In formula (1-2), each Rf independently represents 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. R 1-1 represents a hydrogen atom, a fluorine atom, or a methyl group. 1-2 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

[0075] In formula (1-2), R 1-1 is preferably a hydrogen atom or a methyl group. 1-2 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. Furthermore, Rf in formula (1-1) or formula (1-2) 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.

[0076] The following structures can be exemplified as preferred repeating units made of hydrocarbons having fluorine atoms contained in the fluorine-containing resin in the photosensitive resin composition according to the first embodiment of the present disclosure.

[0077] [ka]

[0078] [ka]

[0079] The content of the repeating unit represented by formula (1-2) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0080] If the content of the repeating unit of formula (1-2) is more than 70 mass%, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (1-2) is less than 5 mass%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0081] Depending on the application, a fluorine-containing resin film can also be formed by a method of applying pressure to the fluorine-containing resin as it is under heat without dissolving it in a solvent (hot pressing method), etc. In this case, even if more than 70 mass % of the repeating unit represented by formula (1-2) is used, the resistance of the fluorine-containing resin as a whole to UV ozone treatment or oxygen plasma treatment and the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment are not deteriorated, and such use is not prohibited in the present disclosure.

[0082] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine-containing resin may contain a structure represented by the following formula (1-3).

[0083] [ka]

[0084] In formula (1-3), R 1-3 , R 1-4 each independently represents a hydrogen atom or a methyl group.

[0085] In formula (1-3), W 1-1 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

[0086] W 1-1When the group is —OC(═O)—NH—, the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment is superior, and this is one of the particularly preferred embodiments.

[0087] In formula (1-3), A 1-1 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3.

[0088] Divalent linking group A 1-1 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 1-1 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 1-1 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 hydroxyl groups, examples of the hydroxyl-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CHOH)CH-), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), a hydroxy-isobutylene group (-CHCH(CHOH)CH-), and a hydroxy-tert-butylene group (-C(CHOH)(CH)CH-).

[0092] Furthermore, when any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, examples of the substituted alkylene group include the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above, in which the hydroxyl groups are replaced with -OC(=O)-CH3.

[0093] Among them, the divalent linking group A 1-1 is preferably 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(CHOH)CH-), a 2-hydroxy-n-butylene group, or a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), more preferably an ethylene group, a propylene group, a 2-hydroxy-n-propylene group, or a hydroxy-isopropylene group (-CH(CHOH)CH-), and particularly preferably an ethylene group or a 2-hydroxy-n-propylene group.

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

[0095] In formula (1-3), n represents an integer of 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are independently ortho, meta or para positions, and preferably para positions.

[0096] The repeating unit represented by formula (1-3) preferably has the following structure: Although the substitution position of the aromatic ring is exemplified as the para position, the substitution position may be independently the ortho position or the meta position.

[0097] The repeating unit represented by formula (1-3) preferably has the following structure: Although the substitution position of the aromatic ring is exemplified as the para position, the substitution position may be independently the ortho position or the meta position.

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] The content of the repeating unit represented by formula (1-3) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0103] If the content of the repeating unit of formula (1-3) is more than 70 mass%, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (1-3) is less than 5 mass%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0104] Although the effect of the repeating unit represented by formula (1-3) according to the first embodiment of the present disclosure is unclear, it is presumed that the repeating unit has resistance to UV ozone treatment or oxygen plasma treatment. However, the present disclosure is not limited to the effects described here.

[0105] As described above, the fluorine-containing resin according to the first embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-3) and another copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-3). In particular, the fluorine-containing resin according to the first embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-3). 1-1 a fluorine-containing resin containing a repeating unit represented by -OC(=O)-NH-; and W in formula (1-3) 1-1 In one preferred embodiment of the present disclosure, the copolymer is a mixture with a fluorine-containing resin containing a repeating unit in which:

[0106] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine-containing resin may contain a structure represented by the following formula (1-4).

[0107] [ka]

[0108] In formula (1-4), R 1-5 , R 1-6 each independently represents a hydrogen atom or a methyl group.

[0109] In formula (1-4), W 1-2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

[0110] W 1-2 is —OC(═O)—NH—, this is one of the particularly preferred embodiments because the fluorine-containing resin according to the first embodiment of the present disclosure has better liquid repellency to ink after UV ozone treatment or oxygen plasma treatment.

[0111] In formula (1-4), A 1-2 , A 1-3 each independently represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3.

[0112] Divalent linking group A 1-2 , A 1-3 are each independently a linear alkylene group having 1 to 10 carbon atoms, examples of which 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.

[0113] Divalent linking group A 1-2 , A 1-3 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.

[0114] Divalent linking group A 1-2 , A 1-3 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.

[0115] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene group include a 1-hydroxyethylene group (-CH(OH)CH-), a 2-hydroxyethylene group (-CHCH(OH)-), a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CHOH)CH-), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), a hydroxy-isobutylene group (-CHCH(CHOH)CH-), and a hydroxy-tert-butylene group (-C(CHOH)(CH)CH-).

[0116] Furthermore, when any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, examples of the substituted alkylene group include the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above, in which the hydroxyl groups are replaced with -OC(=O)-CH3.

[0117] Among them, the divalent linking group A 1-2 , A 1-3 are each independently a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH2OH)CH2-), a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CH 2OH)CH2CH2-), is preferred, with an ethylene group, a propylene group, a 1-hydroxyethylene group (-CH(OH)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, and a hydroxy-isopropylene group (-CH(CH2OH)CH2-) being more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH2-), and a 2-hydroxyethylene group (-CH2CH(OH)-) being particularly preferred.

[0118] In formula (1-4), Y 1-2 , Y 1-3 represents a divalent linking group, each independently representing -O- or -NH-, and more preferably -O-.

[0119] In formula (1-4), n represents an integer of 1 to 3, and n is particularly preferably 1.

[0120] In formula (1-4), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0121] As the repeating unit represented by formula (1-4), the following structures can be exemplified as preferred ones.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] The content of the repeating unit represented by formula (1-4) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0128] If the content of the repeating unit of formula (1-4) is more than 70% by mass, the fluorine-containing resin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (1-4) is less than 5% by mass, the adhesion of the fluorine-containing resin film or bank obtained from the fluorine-containing resin to the substrate tends to decrease.

[0129] Although the effect of the repeating unit represented by formula (1-4) is not clear, it is presumed that the inclusion of the repeating unit represented by formula (1-4) in the fluorine-containing resin improves the adhesion of the resulting fluorine-containing resin film or bank to the substrate, although the present disclosure is not limited to the effects described herein.

[0130] The fluorine-containing resin according to the first embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-4) and another copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-4). In particular, the fluorine-containing resin according to the first embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (1-2) and a repeating unit represented by the formula (1-4). 1-2 a fluorine-containing resin containing a repeating unit represented by -OC(=O)-NH-; and W in formula (1-4) 1-2 In one preferred embodiment of the present disclosure, the copolymer is a mixture with a fluorine-containing resin containing a repeating unit in which:

[0131] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine-containing resin may contain a structure represented by the following formula (1-5).

[0132] [ka]

[0133] In formula (1-5), R 1-7 represents a hydrogen atom or a methyl group.

[0134] In formula (1-5), R 1-8represents 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 repeating unit is 30 mass% or more.

[0135] R 1-8 When 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.

[0136] R 1-8 When is a linear hydrocarbon group, the repeating unit represented by the formula (1-5) is preferably a repeating unit represented by the following formula (1-5-1):

[0137] [ka]

[0138] In formula (1-5-1), R 1-9 is R in equation (1-5). 1-7 is synonymous with.

[0139] In formula (1-5-1), X is a hydrogen atom or a fluorine atom.

[0140] In formula (1-5-1), p is an integer of 1 to 4. q is an integer of 1 to 14. It is particularly preferred that p is an integer of 1 or 2, q is an integer of 2 to 8, and X is a fluorine atom.

[0141] As for the repeating unit represented by formula (1-5), the following structures can be exemplified as preferred ones.

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] The content of the repeating unit represented by formula (1-5) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0147] If the content of the repeating unit of formula (1-5) is more than 70 mass %, the fluorine-containing resin tends to become less soluble in the solvent.

[0148] The repeating unit represented by formula (1-5) is a repeating unit that imparts liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. Therefore, when high liquid repellency to ink is desired, it is preferable that the fluorine-containing resin according to the first embodiment of the present disclosure contains a repeating unit represented by formula (1-5).

[0149] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine-containing resin may contain a structure represented by the following formula (1-6).

[0150] [ka]

[0151] In formula (1-6), R 1-10 represents a hydrogen atom or a methyl group.

[0152] In formula (1-6), B 1are each independently a hydroxyl group, a carboxyl group, -C(=O)-OR 1-11 (R 1-11 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, and R 1-11 The fluorine content in the compound is 30% by mass or more) or -OC(=O)-R 1-12 (R 1-12 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.

[0153] As the repeating unit represented by formula (1-6), the following structures can be exemplified as preferred ones.

[0154] [ka]

[0155] [ka]

[0156] The content of the repeating unit represented by formula (1-6) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 20 to 40% by mass, relative to 100% by mass of the fluororesin.

[0157] If the content of the repeating unit of formula (1-6) is more than 70 mass %, the fluorine-containing resin tends to become less soluble in the solvent.

[0158] In formula (1-6), B 1 is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (1-6) has solubility in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from the fluorine-containing resin, the fluorine-containing resin according to the first embodiment of the present disclosure may contain B 1It is preferable that the repeating unit contains a repeating unit represented by formula (1-6) in which is a hydroxyl group or a carboxyl group.

[0159] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine-containing resin may contain a structure represented by the following formula (1-7).

[0160] [ka]

[0161] In formula (1-7), R 1-13 represents a hydrogen atom or a methyl group.

[0162] In formula (1-7), A 1-4 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3.

[0163] Divalent linking group A 1-4 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.

[0164] Divalent linking group A 1-4 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.

[0165] Divalent linking group A 1-4When 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.

[0166] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene group include a 1-hydroxyethylene group (-CH(OH)CH-), a 2-hydroxyethylene group (-CHCH(OH)-), a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CHOH)CH-), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), a hydroxy-isobutylene group (-CHCH(CHOH)CH-), and a hydroxy-tert-butylene group (-C(CHOH)(CH)CH-).

[0167] Furthermore, when any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, examples of the substituted alkylene group include the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above, in which the hydroxyl groups are replaced with -OC(=O)-CH3.

[0168] Among them, the divalent linking group A 1-4are methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexyl, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH(CH2OH)CH2-), 2-hydroxy-n-butylene, hydroxy-sec-butylene (-CH(CH2OH) Preferred is an ethylene group, a propylene group, a 1-hydroxyethylene group (-CH(OH)CH-), a 2-hydroxyethylene group (-CHCH(OH)-), a 2-hydroxy-n-propylene group, or a hydroxy-isopropylene group (-CH(CHOH)CH-), and particularly preferred is an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH-), or a 2-hydroxyethylene group (-CHCH(OH)-).

[0169] In formula (1-7), Y 1-4 represents a divalent linking group, and represents -O- or -NH-, and more preferably -O-.

[0170] In formula (1-7), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0171] In formula (1-7), E 1-1 represents a hydroxyl group, a carboxyl group, or an oxirane group. E 1-1 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.

[0172] In formula (1-7), s represents 0 or 1. When s is 0, (-Y 1-4 -A 1-4 -) represents a single bond. When r is 0 and s is 0, the main chain of the repeating unit does not contain E 1-1 The resulting structure is a bonded structure.

[0173] As the repeating unit represented by formula (1-7), the following structures can be exemplified as preferred ones.

[0174] [ka]

[0175] In formula (1-7), E 1-1 is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (1-7) imparts solubility to the fluorine-containing resin in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from the fluorine-containing resin, the fluorine-containing resin according to the first embodiment of the present disclosure is 1-1 It is preferable that the repeating unit contains a repeating unit represented by formula (1-7) in which is a hydroxyl group or a carboxyl group.

[0176] In the photosensitive resin composition according to the first embodiment of the present disclosure, the molecular weight of the fluorine-containing resin is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and particularly preferably 3,000 or more and 100,000 or less, as a weight-average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as the standard substance. If the molecular weight is less than 1,000, the strength of the fluorine-containing resin film or bank for organic EL devices that is formed tends to decrease, while if the molecular weight is more than 1,000,000, the solubility in solvents is insufficient, making it difficult to form a fluorine-containing resin film by coating.

[0177] The dispersity (Mw / Mn) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, and particularly preferably from 1.01 to 3.00.

[0178] The fluorine-containing resin 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.

[0179] Preferred embodiments of the fluorine-containing resin in the photosensitive resin composition according to the first embodiment of the present disclosure are as follows. <Aspect 1-1> A fluorine-containing resin containing both a repeating unit represented by the following formula (1-2) and a repeating unit represented by the following formula (1-3): Formula (1-2):R 1-1 and R 1-2 is a hydrogen atom, and each Rf is independently a fluorine atom, a difluoromethyl group, or a trifluoromethyl group. Formula (1-3):R 1-3 and R 1-4 is a hydrogen atom, W 1 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 1-1 is an ethylene group, Y 1-1 is -O-, n is 1

[0180] <Aspect 1-2> A fluorine-containing resin containing both a repeating unit represented by the following formula (1-2) and a repeating unit represented by the following formula (1-3): Formula (1-2): Same as embodiment 1-1 Formula (1-3):R 1-3 and R 1-4 is a hydrogen atom, W 1-1 -O-, A 1-1 is a 2-hydroxy-n-propylene group or a hydroxy-isopropylene group (-CH(CHOH)CH-), Y 1-1 is -O-, n is 1

[0181] <Aspect 1-3> Fluorine-containing resins containing repeating units represented by the following formulas (1-2), (1-3) and (1-5-1): Formula (1-2): Same as embodiment 1-1 Formula (1-3): Same as embodiment 1-1 Formula (1-5-1):R 1-9 is a methyl group, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom

[0182] <Aspect 1-4> Fluorine-containing resins containing repeating units represented by the following formulas (1-2), (1-3), (1-5-1) and (1-6): Formula (1-2): Same as embodiment 1-1 Formula (1-3): Same as embodiment 1-1 Formula (1-5-1): Same as embodiment 1-3 Formula (1-6):R 1-10 is a hydrogen atom, B 1 is a hydroxyl group or a carboxyl group, m is 1

[0183] <Aspect 1-5> A fluorine-containing resin containing both a repeating unit represented by the following formula (1-2) and a repeating unit represented by the following formula (1-4): Formula (1-2): Same as embodiment 1-1 Formula (1-4):R 1-5 and R 1-6 are each independently a hydrogen atom or a methyl group, W 1-2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 1-2 , A 1-3 are each independently an ethylene group, Y 1-2 and Y 1-3 is -O-, n is 1, r is 1

[0184] <Aspect 1-6> A fluorine-containing resin containing both a repeating unit represented by the following formula (1-2) and a repeating unit represented by the following formula (1-4): Formula (1-2): Same as embodiment 1-1 Formula (1-4):R 1-5 and R 1-6 are each independently a hydrogen atom or a methyl group, W 1-2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 1-2 , A 1-3 are each independently an ethylene group, a 1-hydroxy-n-ethylene group (-CH(OH)CH2-) or a 2-hydroxy-n-ethylene group (-CH2CH(OH)-), Y 1-2 and Y 1-3 is -O-, n is 1, r is 1

[0185] <Aspect 1-7> A fluorine-containing resin containing both a repeating unit represented by the following formula (1-2) and a repeating unit represented by the following formula (1-4): Formula (1-2): Same as embodiment 1-1 Formula (1-4):R 1-5 and R 1-6 are each independently a hydrogen atom or a methyl group, W 1-2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 1-2 , A 1-3 each independently represents an ethylene group or a butyl group; Y 1-2 and Y 1-3 is -O-, n is 1, r is 0

[0186] <Aspect 1-8> Fluorine-containing resins containing repeating units represented by the following formulas (1-2), (1-4) and (1-5-1): Formula (1-2): Same as embodiment 1-1 Formula (1-4): Same as embodiment 1-5 Formula (1-5-1): Same as embodiment 1-3

[0187] <Aspect 1-9> Fluorine-containing resins containing repeating units represented by the following formulas (1-2), (1-4), (1-5-1) and (1-7): Formula (1-2): Same as embodiment 1-1 Formula (1-4): Same as embodiment 1-5 Formula (1-5-1): Same as embodiment 1-3 Formula (1-7):R 1-13 is a hydrogen atom, A 1-4 is an ethylene group, Y 1-4 is -O-, r is 1, s is 1, E 1-1 is a hydroxyl or carboxyl group

[0188] <Aspect 1-10> Fluorine-containing resins containing repeating units represented by the following formulas (1-2), (1-4), (1-5-1), (1-6) and (1-7): Formula (1-2): Same as embodiment 1-1 Formula (1-4): Same as embodiment 1-5 Formula (1-5-1): Same as embodiment 1-3 Formula (1-6): Same as embodiment 1-4 Formula (1-7): Same as embodiment 1-9

[0189] In the photosensitive resin composition according to the first embodiment of the present disclosure, the fluorine content of the fluororesin is preferably 20 to 50% by mass, and more preferably 25 to 40% by mass. If the fluorine content is within this range, the resin is easily dissolved in a solvent. When the fluorine-containing resin contains fluorine atoms, a fluorine-containing resin film or bank having excellent liquid repellency can be obtained.

[0190] In this specification, the "fluorine content of the fluororesin" can be calculated from the molar ratio of the monomers constituting the fluororesin measured by NMR (nuclear magnetic resonance spectroscopy), the molecular weight of the monomers constituting the fluororesin, the fluorine content contained in the monomers, etc. Here, a method for measuring the fluorine content when the fluororesin is a resin made of 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate will be described. (i) First, the proportion of each component is calculated (molar proportion) by measuring the fluororesin by NMR. (ii) Multiply the molecular weight (Mw) of the monomer in each component of the fluororesin by the molar ratio, add up the resulting values, and calculate the weight percentage (wt%) of each component from the total. The molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 1,1-bistrifluoromethylbutadiene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432. (iii) Next, for the composition containing fluorine, the fluorine content in the monomer is calculated. (iv) Calculate the "fluorine content in the monomer ÷ monomer molecular weight (Mw) × weight percentage (wt%)" for each component, and add up the obtained values. (v) Calculate the fluorine content of the fluororesin by dividing the value obtained in (iv) above by the total value obtained in (ii) above.

[0191] <Solvent> In the photosensitive resin composition according to the first embodiment of the present disclosure, the solvent is not particularly limited as long as it dissolves the fluorine-containing resin, and examples thereof include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, fluorine-containing solvents, etc. These may be used alone or in combination of two or more.

[0192] Specific examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. Specific 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.

[0193] Specific 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), and the monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0194] Specific examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0195] Specific 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. Examples of aromatic solvents include xylene and toluene.

[0196] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0197] 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.

[0198] Among them, the solvents are 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 The solvent is preferably at least one selected from the group consisting of propylene glycol 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. Methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone are more preferred.

[0199] The amount of solvent in the photosensitive resin composition according to the first embodiment of the present disclosure is preferably in the range of 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the fluorine-containing resin concentration (however, when the photosensitive resin composition contains an alkali-soluble resin, which will be described later, the combined concentration of the resin). By adjusting the amount of solvent, the thickness of the resin film to be formed can be adjusted, and within the above range, a resin film thickness particularly suitable for obtaining a bank for organic electroluminescence can be obtained.

[0200] <Photopolymerization initiator> In the photosensitive resin composition according to the first embodiment of the present disclosure, the photopolymerization initiator is not particularly limited as long as it polymerizes a monomer having a polymerizable double bond by high-energy rays such as electromagnetic waves or electron beams, and any known photopolymerization initiator can be used. As the photopolymerization initiator, a photoradical initiator or a photoacid initiator can be used, and these may be used alone, or a photoradical initiator and a photoacid initiator may be used in combination, or two or more types of photoradical initiators or photoacid initiators may be mixed and used. Furthermore, by using an additive together with the photopolymerization initiator, it is also possible to carry out living polymerization in some cases, and known additives can be used as the additive.

[0201] Photoradical initiators can be specifically classified into intramolecular cleavage types in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction types in which radicals are generated in combination with a hydrogen donor such as a tertiary amine or ether, and either type may be used. Photoradical initiators other than those types listed above may also be used.

[0202] Specific examples of the photoradical initiator include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based initiators.

[0203] Specific examples of benzophenone-based compounds 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.

[0204] Specific examples of acetophenone-based compounds 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.

[0205] Specific examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylformate, and 9,10-phenanthrenequinone, among which 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0206] Specific examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0207] Specific examples of quinones include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0208] Specific examples of acyloin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Of these, benzoin and benzoin methyl ether are preferred.

[0209] As the photoradical initiator, benzophenone-based, acetophenone-based and diketone-based initiators are preferred, and benzophenone-based initiators are more preferred.

[0210] Among commercially available photoradical initiators, preferred ones include the following product names manufactured by BASF Co., Ltd.: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Lugacure 907, Irgacure 2959, Irgacure OXE-01, Darocur 1173, Lucilin TPO, etc. Among these, Irgacure 651 and Irgacure 369 are more preferred.

[0211] Specifically, the photoacid initiator is an onium salt consisting of a pair of at least one cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, and (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. Among these, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0212] Examples of commercially available photoacid generators include those manufactured by San-Apro Co., Ltd. under the product names CPI-100P, CPI-110P, CPI-101A, CPI-200K, and CPI-210S; those manufactured by Dow Chemical Japan under the product names Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, and Cyracure Photocuring Initiator UVI-6976; and those manufactured by ADEKA Corporation under the product names ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, and ADEKA Optomer SP -172, Adeka Optomer SP-300, Nippon Soda Co., Ltd. product names: CI-5102, CI-2855, Sanshin Chemical Industry Co., Ltd. product names: San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110, San-Aid SI-180, Lamberti product names: Esacure 1064, Esacure 1187, and Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 250.

[0213] The content of the photopolymerization initiator in the photosensitive resin composition according to the first embodiment of the present disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains an alkali-soluble resin, which will be described later, the concentration of the resins combined). If the content of the photopolymerization initiator is less than 0.1 part by mass, the crosslinking effect tends to be insufficient, whereas if it exceeds 30 parts by mass, the resolution and sensitivity tend to decrease.

[0214] The photosensitive resin composition according to the first embodiment of the present disclosure may contain, in addition to the essential components of a fluorine-containing resin, a solvent, and a photopolymerization initiator, a crosslinking agent, an alkali-soluble resin, a naphthoquinone diazide group-containing compound, a basic compound, and other additives.

[0215] <Crosslinking agent> The crosslinking agent reacts with the repeating unit represented by formula (1-3) or formula (1-4) to allow the resin to adopt a crosslinked structure, thereby improving the mechanical strength of the film formed.

[0216] Known crosslinking agents can be used, specifically, compounds in which an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, propyleneurea, or glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol, and the hydrogen atom of the amino group is substituted with a hydroxymethyl group or a lower alkoxymethyl group, polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyfunctional isocyanate compounds, polyfunctional acrylate compounds, etc. Here, those using melamine are called melamine-based crosslinking agents, those using urea are called urea-based crosslinking agents, those using alkylene ureas such as ethyleneurea and propyleneurea are called alkylene urea-based crosslinking agents, and those using glycoluril are called glycoluril-based crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.

[0217] The crosslinking agent is preferably at least one selected from these crosslinking agents, and glycoluril-based crosslinking agents and polyfunctional acrylate compounds are particularly preferred.

[0218] Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine, with hexamethoxymethylmelamine being preferred.

[0219] Examples of the urea-based crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among these, bismethoxymethylurea is preferred.

[0220] Examples of alkylene urea-based crosslinking agents include ethylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0221] Examples of glycoluril crosslinking agents include mono-, di-, tri-, and / or tetrahydroxymethylated glycoluril, mono-, di-, tri-, and / or tetramethoxymethylated glycoluril, mono-, di-, tri-, and / or tetraethoxymethylated glycoluril, mono-, di-, tri-, and / or tetrapropoxymethylated glycoluril, and mono-, di-, tri-, and / or tetrabutoxymethylated glycoluril.

[0222] Examples of the polyfunctional acrylate compound include polyfunctional acrylates (for example, product names A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol diacrylates (for example, product names A-200, A-400, and A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.), urethane acrylates (for example, product names UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, and UA-7200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and pentaerythritol tetraacrylate.

[0223] Preferred examples of the polyfunctional acrylate compound are shown below.

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] The content of the crosslinking agent in the photosensitive resin composition according to the first embodiment of the present disclosure is preferably 10 parts by mass or more and 300 parts by mass or less, and more preferably 50 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains an alkali-soluble resin described below, the concentration of the resins combined). If the content of the crosslinking agent is less than 10 parts by mass, the crosslinking effect tends to be insufficient, whereas if it exceeds 300 parts by mass, the resolution and sensitivity tend to decrease.

[0228] <Alkali-soluble resin> When the photosensitive resin composition according to the first embodiment of the present disclosure contains an alkali-soluble resin, the shape of the bank obtained from the photosensitive resin composition according to the first embodiment of the present disclosure can be improved.

[0229] The alkali-soluble resin may be an alkali-soluble novolak resin. The alkali-soluble novolak resin can be obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst.

[0230] 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-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more.

[0231] 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 the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, etc. These acid catalysts may be used alone or in combination of two or more.

[0232] Other examples of alkali-soluble resins include acid-modified epoxy acrylates. Commercially available acid-modified epoxy acrylates 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.

[0233] The weight average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive resin composition.

[0234] The content of the alkali-soluble resin in the photosensitive resin composition according to the first embodiment of the present disclosure is preferably 500 parts by mass or more and 10,000 parts by mass or less, and more preferably 1,000 parts by mass or more and 7,000 parts by mass or less, relative to 100 parts by mass of the fluororesin. If the content of the alkali-soluble resin exceeds 10,000 parts by mass, the ink repellency after UV ozone treatment or oxygen plasma treatment that the fluororesin according to the first embodiment of the present disclosure has tends to be insufficient.

[0235] <Naphthoquinone diazide group-containing compounds> When the photosensitive resin composition according to the first embodiment of the present disclosure contains a naphthoquinone diazide group-containing compound, the shape of the bank obtained from the photosensitive resin composition according to the first embodiment of the present disclosure can be improved. The naphthoquinone diazide group-containing compound is not particularly limited, and any compound that is commonly used as a photosensitive component in an i-line resist composition can be used.

[0236] Specific examples of naphthoquinone diazide group-containing compounds include naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds, naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid ester compounds, and orthoanthraquinone diazide sulfonic acid ester compounds. Among these, naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, and naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds are preferred due to their excellent solubility. These compounds may be used alone or in combination of two or more.

[0237] The content of the naphthoquinone diazide group-containing compound in the photosensitive resin composition according to the first embodiment of the present disclosure is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains the alkali-soluble resin, the concentration of the resin in total). If the content exceeds 60 parts by weight, it tends to be difficult to obtain the sensitivity required for the photosensitive resin composition.

[0238] <Basic compounds> The basic compound has the function of slowing down the diffusion rate of the acid generated by the photoacid generator when it diffuses into the film of the photosensitive resin composition according to the first embodiment of the present disclosure. By adding a basic compound, the acid diffusion distance can be adjusted, and the shape of the bank can be improved. Furthermore, by incorporating a basic compound, the banks are less likely to deform even if the time required for leaving the banks after their formation before exposure is long, and banks of the desired precision can be stably formed.

[0239] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, and specific examples include secondary or tertiary aliphatic amines and alkyl alcohol amines. These basic compounds may be used alone or in combination of two or more.

[0240] Examples of aliphatic amines include alkylamines or alkyl alcoholamines in which at least one hydrogen atom of ammonia (NH3) has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, and di-n-octylamine. Examples of such amines include n-nonylamine, di-n-decanylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decanylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, and alkyl alcoholamines are more preferred. Among the alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0241] Examples of aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; heterocyclic amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, and 4,4-dimethylimidazoline; ,6-pentamethyl-4-piperidyl) sebagate and other hindered amines; 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine and other alcoholic nitrogen-containing compounds; picoline, lutidine, pyrrole, piperidine, piperazine, indole, hexamethylenetetramine and the like.

[0242] In the photosensitive resin composition according to the first embodiment of the present disclosure, the content of the basic compound is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains the alkali-soluble resin, the concentration of the resin combined). If the amount of the basic compound is less than 0.001 part by mass, it becomes difficult to obtain a sufficient effect as an additive, and if it exceeds 2 parts by mass, resolution and sensitivity tend to decrease.

[0243] <Other additives> The photosensitive resin composition according to the first embodiment of the present disclosure may contain other additives as needed, such as a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a surfactant, a thickener, a leveling agent, an antifoaming agent, a compatibilizer, an adhesion agent, and an antioxidant. These other additives may be known ones.

[0244] The surfactant preferably contains either a fluorine-based or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom), or two or more of these.

[0245] Next, a method for producing a cured fluorine-containing resin product using the photosensitive resin composition according to the first embodiment of the present disclosure will be described.

[0246] The method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure is characterized by including a baking step of curing the photosensitive resin composition according to the first embodiment of the present disclosure by baking at a temperature of 140°C or less. In this step, it is desirable to bake the photosensitive resin composition according to the first embodiment of the present disclosure at a temperature of 60 to 130°C.

[0247] Furthermore, the method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure may include, before the baking step, an exposure step of exposing the photosensitive resin composition to high-energy rays. The high-energy rays are preferably at least one type selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0248] The fluorine-containing resin cured product obtained in this manner has excellent water and oil repellency due to its low surface free energy, and can be used as a material to protect substrates in a variety of applications, such as a water and oil repellent agent for treating fabrics (substrates) for clothing, etc., or a sealant for protecting microfabricated semiconductor substrates (substrates).

[0249] Furthermore, the method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure may include (1-1) a film-forming step, (1-2) an exposure step, (1-3) a development step, and (1-4) a baking step. Each step will be explained below.

[0250] (1-1) Film formation process First, the photosensitive resin composition according to the first embodiment of the present disclosure is applied to a substrate and then heated to convert the photosensitive resin composition into a fluorine-containing resin film. The heating conditions are not particularly limited, but preferably are 80 to 100° C. and 60 to 200 seconds. This makes it possible to remove the solvent and the like contained in the photosensitive resin composition.

[0251] The substrate may be a silicon wafer, metal, glass, ITO substrate, or the like. An organic or inorganic film may be previously formed on the substrate. For example, an anti-reflective film or a lower layer of a multilayer resist may be present, and a pattern may be formed on the film. The substrate may also be pre-washed. For example, it can be washed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), etc.

[0252] As a method for applying the photosensitive resin composition according to the first embodiment of the present disclosure to a substrate, a known method such as spin coating can be used.

[0253] (1-2) Exposure process Next, a desired photomask is set in an exposure device, and the fluorine-containing resin film is exposed to high-energy rays through the photomask. The high-energy ray is preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0254] The exposure dose of high-energy rays is 1 mJ / cm 2 More than 200mJ / cm 2 Preferably, it is 10 mJ / cm or less. 2 More than 100mJ / cm 2 More preferably, it is:

[0255] (1-3)Developing process Next, the fluorine-containing resin film after the exposure step is developed with an alkaline aqueous solution to form a fluorine-containing resin pattern film. That is, either the exposed portion of the fluorine-containing resin film or the unexposed portion of the film is dissolved in an alkaline aqueous solution to form a patterned fluorine-containing resin film.

[0256] As the alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), or the like can be used. When the alkaline aqueous solution is a tetramethylammonium hydroxide (TMAH) aqueous solution, its concentration is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 2% by mass or more and 3% by mass or less.

[0257] As the developing method, a known method can be used, for example, a dipping method, a puddle method, a spray method, or the like.

[0258] The development time (the time during which the developer is in contact with the fluorine-containing resin film) is preferably from 10 seconds to 3 minutes, more preferably from 30 seconds to 2 minutes.

[0259] After development, if necessary, a step of washing the fluorine-containing resin patterned film with deionized water, etc. The washing method and washing time are preferably from 10 seconds to 3 minutes, and more preferably from 30 seconds to 2 minutes.

[0260] (1-4) Baking process After the developing step, the fluorine-containing resin pattern film is cured by baking at a temperature of 140° C. or less to form a cured fluorine-containing resin product. Baking can be carried out on a hot plate, and the baking conditions are preferably 60 to 130° C. and 10 to 120 minutes.

[0261] The fluorine-containing resin cured product thus produced can be used as a bank for organic EL displays, micro LED displays, quantum dot displays, etc. That is, the method for producing a cured fluorine-containing resin material according to the first embodiment of the present disclosure can also be used to produce banks for organic EL displays, micro LED displays, quantum dot displays, and the like. In the method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure, the photosensitive resin composition can be cured at a low temperature. Therefore, when producing a bank for an organic electroluminescence display, a micro LED display, a quantum dot display, or the like, by the method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure, the bank can be formed without causing significant thermal damage to the light-emitting layer.

[0262] In the method for producing a cured fluorine-containing resin product according to the first embodiment of the present disclosure, a UV ozone treatment or an oxygen plasma treatment may be carried out after the baking step (1-4). Of these, the UV ozone treatment is preferred. This makes it possible to remove organic matter remaining in the recesses of the fluorine-containing resin pattern film, and reduces uneven wetting of the dropped ink, thereby preventing defects in the display element.

[0263] (Example according to the first embodiment) Hereinafter, the aspects of the first embodiment of the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these embodiments.

[0264] 1. Synthesis of Monomers [Synthesis Example 1-1] Synthesis of 1,1-Bistrifluoromethylbutadiene (BTFBE) 400 g of concentrated sulfuric acid was added to a 1000 ml glass flask equipped with a stirrer, and after heating to 100 °C, 300 g of 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol was gradually added dropwise over 1 hour. After completion of the dropwise addition, stirring was carried out at 100 °C for 60 minutes, and the reaction solution was 19 analyzed by F-NMR, and no residual raw materials were detected. Next, a fraction with a boiling point of 68 - 70 °C was recovered from the reaction solution by atmospheric distillation, and 1,1-bistrifluoromethylbutadiene (hereinafter referred to as BTFBE) was obtained in a yield of 58%. It is considered that the following chemical reaction occurs in this reaction.

[0265]

Chemical formula

[0266] <NMR Analysis Results> When the synthesized BTFBE was analyzed by NMR, the following results were obtained. 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 5.95 (1H, dd) 6.05 (1H, dd), 6.85 (1H, m), 7.04 (1H, m) 19 F-NMR (solvent: deuterated chloroform, reference substance: C6D6); δ (ppm) -65.3 (3F, m), -58.4 (3F, m)

[0267] [Synthesis Example 1-2] Synthesis of 4-Hydroxystyrene (p-HO-St) In a 1000 ml glass flask equipped with a stirrer, 100 g of p-acetoxystyrene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St) and 300 g of methanol were mixed at room temperature (approximately 20°C), and 0.50 g of 1,3,5-trihydroxybenzene (equivalent to 0.5 mass% of p-AcO-St) was added as a polymerization inhibitor. Next, this solution was cooled to 0°C in an ice bath, and then a 12 mass% aqueous sodium hydroxide solution (equivalent to 1.0 equivalent of p-AcO-St) was gradually added dropwise over 40 minutes, followed by stirring at 0°C for 30 minutes. The reaction solution was 1 Analysis by H-NMR revealed that no residual raw materials were detected. Next, an 18% by mass aqueous hydrochloric acid solution (equivalent to 0.8 equivalents of p-AcO-St) was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes after the addition. The pH of this solution was measured and found to be 6. The resulting reaction solution was extracted with 360 g of methyl t-butyl ether at room temperature (approximately 20°C). It was then washed twice with 330 g of purified water. 1,3,5-trihydroxybenzene was added to the resulting organic layer in an amount equivalent to 1% by mass of 4-hydroxystyrene. The 4-hydroxystyrene was then concentrated to 72% by mass and poured into n-octane, a poor solvent, cooled to 0°C. The solution was then immersed in an ice bath and stirred for 1 hour to precipitate 4-hydroxystyrene crystals. The crystals were filtered and further washed with n-octane. The crystals were then dried under reduced pressure at 25°C to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield: 66%). In this reaction, the following chemical reaction is thought to occur:

[0268] [ka]

[0269] 2. Production of Fluorine-Containing Resin (First Step: Polymerization) [Measurement of the molar ratio of each repeating unit] NMR The molar ratio of each repeating unit in the polymer is 1 H-NMR, 19 F-NMR or13 It was determined from the measurement values of \(^{13}\)C-NMR. [Measurement of Polymer Molecular Weight] GPC The weight average molecular weight Mw and the molecular weight distribution (the ratio of the number average molecular weight Mn to the weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, model HLC-8320GPC), connecting one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) in series, using tetrahydrofuran (THF) as the eluent, and using polystyrene as the standard substance. A differential refractive index detector was used as the detector.

[0270] 2-1. Polymerization of Fluorine-containing Resin Precursor [Synthesis of Fluorine-containing Resin Precursor 1-1] At room temperature (about 20 °C) in a 300 ml glass flask equipped with a stirrer, 9.5 g (0.05 mol) of BTFBE obtained in Synthesis Example 1-1, 13.1 g (0.10 mol) of 2-hydroxyethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HEMA), 43.2 g (0.1 mol) of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C6F), 9.0 g (0.075 mol) of p-HO-St obtained in Synthesis Example 1-2, 70 g of MEK were taken, 1.6 g (0.005 mol) of 2,2'-azobis(2-methylbutyronitrile) (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was added, and after degassing with stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 75 °C and reacted for 6 hours. When 380 g of n-heptane was dropped into the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. Vacuum drying was carried out at 60 °C to obtain 67 g of a fluorine-containing resin precursor 1-1 as a transparent viscous substance with a yield of 9%.

[0271] <NMR Measurement Results> When the fluorine-containing resin precursor 1-1 was analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of the fluorine-containing resin precursor 1-1" was: repeating unit by BTFBE: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by p-HO-St = 20:28:30:22.

[0272]

Chemical formula

[0273] <GPC measurement results> As a result of measuring the fluorine-containing resin precursor 1-1 by GPC, Mw was 6,700 and Mw / Mn was 1.3.

[0274] [Synthesis of fluorine-containing resin precursor 1-2] A fluorine-containing resin precursor 1-2 containing the following repeating units was obtained in a yield of 91% by the same procedure as the synthesis of the fluorine-containing resin precursor 1-1, except that vinyl benzoic acid (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as VBA) was used instead of p-HO-St.

[0275] <NMR measurement results> When the fluorine-containing resin precursor 1-2 was analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of the fluorine-containing resin precursor 1-2" was: repeating unit by BTFBE: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by VBA = 19:27:31:23.

[0276]

Chemical formula

[0277] <GPC measurement results> As a result of measuring the fluorine-containing resin precursor 1-2 by GPC, Mw was 6,900 and Mw / Mn was 1.3.

[0278] [Synthesis of fluorine-containing resin precursor 1-3] A fluorine-containing resin precursor 1-3 containing the following repeating units was obtained in a yield of 88% by the same procedure as the synthesis of the fluorine-containing resin precursor 1-1, except that p-acetoxystyrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St) was used instead of p-HO-St.

[0279] <NMR measurement results> When the fluorine-containing resin precursor 1-3 was analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of the fluorine-containing resin precursor 1-3" was: repeating unit by BTFBE: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by p-AcO-St = 15:33:30:22.

[0280]

Chemical formula

[0281] <GPC measurement results> As a result of measuring the fluorine-containing resin precursor 1-3 by GPC, Mw was 7,100 and Mw / Mn was 1.3.

[0282] [Synthesis of fluorine-containing resin precursor 1-4] A fluorine-containing resin precursor 1-4 containing the following repeating units was obtained in a yield of 90% by the same procedure as the synthesis of the fluorine-containing resin precursor 1-1, except that styrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as St) was used instead of p-HO-St.

[0283] <NMR measurement results> When the fluorine-containing resin precursor 1-4 was analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of the fluorine-containing resin precursor 1-4" was: repeating unit by BTFBE: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by St = 16:34:29:21.

[0284]

Chemical formula

[0285] <GPC measurement results> As a result of subjecting fluorine-containing resin precursors 1-4 to GPC measurement, Mw was 7,400 and Mw / Mn was 1.3.

[0286] [Synthesis of fluorine-containing resin precursors 1-5] In a 300 ml glass flask equipped with a stirrer, at room temperature, 13.01 g (0.1 mol) of HEMA, 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of hexafluoro-2-propyl methacrylate (HFIP-M), 8.66 g (0.1 mol) of methyl methacrylate (MAA), and 88 g of MEK were taken. 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, heated to 80 °C, and then reacted for 6 hours. The reaction solution after completion of the reaction was dropped into 530 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 60 g of fluorine-containing resin precursor 5 as a white solid with a yield of 66%.

[0287] <NMR measurement results> When fluorine-containing resin precursors 1-5 were analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of fluorine-containing resin precursors 1-5" was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by HFIP-M: repeating unit by MAA = 25:25:24:26.

[0288] [Chemical formula]

[0289] <GPC measurement results> As a result of subjecting fluorine-containing resin precursors 1-5 to GPC measurement, Mw was 10,300 and Mw / Mn was 1.4.

[0290] [Synthesis of fluorine-containing resin precursors 1-6] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 13.1 g (0.10 mol) of HEMA, 43.2 g (0.10 mol) of MA-C6F, 11.1 g (0.075 mol) of VBA, and 75 g of MEK were taken. 1.6 g (0.005 mol) of 2,2'-azobis(2-methylbutyronitrile) (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 75 °C and reacted for 6 hours. When 400 g of n-heptane was dropped into the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. Vacuum drying was carried out at 60 °C to obtain 56 g of a fluorine-containing resin precursor 1-6 as a transparent viscous substance with a yield of 83%.

[0291] <NMR Measurement Results> When the fluorine-containing resin precursor 1-6 was analyzed by NMR, the composition ratio (mol ratio) of the following "each repeating unit of the fluorine-containing resin precursor 1-6" was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by VBA = 33:32:35.

[0292] [Chemical Structure]

[0293] <GPC Measurement Results> As a result of measuring the fluorine-containing resin precursor 1-6 by GPC, Mw was 14,300 and Mw / Mn was 1.6.

[0294] 2-2. Synthesis of Comparative Fluorine-Containing Resin Precursors [Comparative Polymerization Example 1-1] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 13.1 g (0.10 mol) of HEMA, 43.2 g (0.1 mol) of MA-C6F, 14.2 g (0.1 mol) of normal butyl methacrylate (hereinafter abbreviated as MA-nBu), 71 g of MEK were taken, 0.8 g (0.005 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and after heating to 80 °C, the reaction was carried out for 6 hours. The reaction solution after the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 49.3 g of a fluorine-containing resin precursor 1-1 as a white solid with a yield of 70%.

[0295] <NMR measurement results> When the fluorine-containing resin precursor 1-1 was analyzed by NMR, the composition ratio (mol ratio) of the following "repeating units of the fluorine-containing resin precursor 1-1" was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by MA-nBu = 35:32:33.

[0296]

Chemical formula

[0297] <GPC measurement results> As a result of measuring the fluorine-containing resin precursor 1-1 by GPC, Mw was 10,700 and Mw / Mn was 1.7.

[0298] [Comparative polymerization example 1-2] A comparative fluorine-containing resin precursor 1-2 containing the following repeating units was obtained in a yield of 74% by the same procedure as the synthesis of the comparative fluorine-containing resin precursor 1-1, except that p-AcO-St was used instead of MA-nBu.

[0299] <NMR measurement results><NMR measurement results> When the fluorine-containing resin precursor 1-2 was analyzed by NMR, the composition ratio (mol ratio) of "each repeating unit of the fluorine-containing resin precursor 1-2" was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by p-AcO-St = 33:34:33.

[0300]

Chemical formula

[0301] <GPC measurement results> As a result of measuring the fluorine-containing resin precursor 1-2 by GPC, Mw was 15,300 and Mw / Mn was 1.7.

[0302] [Comparative polymerization example 1-3] A comparative fluorine-containing resin precursor 1-3 containing the following repeating units was obtained in a yield of 75% by the same procedure as the synthesis of the comparative fluorine-containing resin precursor 1-1, except that p-HO-St was used instead of MA-nBu.

[0303] <NMR measurement results> When the comparative fluorine-containing resin precursor 1-3 was analyzed by NMR, the composition ratio (mol ratio) of "each repeating unit of the comparative fluorine-containing resin precursor 1-3" was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by p-HO-St = 34:32:34.

[0304]

Chemical formula

[0305] <GPC measurement results> As a result of measuring the comparative fluorine-containing resin precursor 1-3 by GPC, Mw was 12,300 and Mw / Mn was 1.6.

[0306] The repeating units, molar ratios, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), yield, and fluorine content (%) contained in each of the obtained fluororesin precursors and each of the comparative fluororesin precursors are shown in Table 1-1. The fluorine content was determined by calculating the weight ratio from the molar ratio of the repeating units of each monomer after polymerization, and then calculating the weight ratio of fluorine atoms in each monomer constituent.

[0307] [Table 1-1]

[0308] 3. Production of Fluorine-Containing Resin (Second Step: Addition Reaction) Fluorine-containing resins were synthesized by reacting each of the fluorine-containing resin precursors and each of the comparative fluorine-containing resin precursors obtained in "2. Production of fluorine-containing resins (first step: polymerization)" with an acrylic acid derivative. 2-Isocyanatoethyl acrylate (product name: Karenz-AOI, product of Showa Denko K.K.) represented by the following chemical formula was used as the acrylic acid derivative. This reaction is an addition reaction between the hydroxyl group in each of the fluorine-containing resin precursors and the acrylic acid derivative. Examples of the synthesis of each fluorine-containing resin are described below, and the names of the obtained fluorine-containing resins are as follows. The first number indicates the number of the fluororesin precursor, the following alphabet indicates the acrylic acid derivative used, and when Karenz-AOI was used, it is "A". The final number in parentheses indicates the nominal amount (molar ratio) of the acrylic acid derivative introduced to each resin precursor.

[0309] [ka]

[0310] [Synthesis of Fluorine-Containing Resin 1-1-A(100)] In a 300 ml glass flask equipped with a stirrer, 10 g (hydroxyl equivalent 0.0115 mol) of the fluororesin precursor 1-1, 30 g of PGMEA were taken, 1.62 g (0.0114 mol) of KARENZ-AOI was added, and the reaction was carried out at 45 °C for 8 hours. After the reaction solution after the reaction was concentrated, 150 g of n-heptane was added to precipitate a precipitate. This precipitate was filtered off and dried under reduced pressure at 35 °C to obtain 11.1 g of fluororesin 1-1-A(100) as a white solid with a yield of 95%.

[0311] <NMR measurement results> In the fluororesin 1-1-A(100), the introduced amount (reaction rate) of the acrylic acid derivative derived from KARENZ-AOI and the amount of residual hydroxyl groups (unreacted rate), expressed in mol ratio, were 99:1. Also, it was confirmed that the composition ratios of each repeating unit (repeating unit by BTFBE, repeating unit by MA-C6F, and repeating unit by p-HO-St) that do not react with the crosslinking group site did not change from the used fluororesin precursor 1-1 (the same as before the introduction of the crosslinking group). Also, the newly formed bond (W in formula (4)) 2 ) was “-O-C(=O)-NH-”.

[0312] [Synthesis of fluororesins 1-2-A(100) to 1-6-A(100) and comparative fluororesins 1-1-A(100) to 1-3-A(100)] Similar to the fluororesin 1-1-A(100), fluororesins 1-2-A(100) to 1-6A(100) and comparative fluororesins 1-1-A(100) to 1-3-A(100) were synthesized. The used fluororesin precursors, acrylic acid derivatives, formed crosslinking group structures (W in the above formula (1-4)) 1-2 ), the introduced amount of the crosslinking group (reaction rate), the amount of residual hydroxyl groups (unreacted rate), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) are shown in Table 1-2.

[0313]

Table of 1-2

[0314] 4. Low-temperature curing evaluation of each fluororesin cured film [Formation of fluorine-containing photocurable resin compositions 1-1 to 1-6 and comparative fluorine-containing photocurable resin compositions 1-1 to 1-3] 10 parts of each of the produced fluorine-containing resins or comparative fluorine-containing resins, 75 parts of solvent, 5 parts of photopolymerization initiator, and 10 parts of crosslinking agent were mixed, and the resulting solution was filtered through a 0.2 μm membrane filter to prepare fluorine-containing curable resin compositions 1-1 to 1-6 and comparative fluorine-containing curable resin compositions 1-1 to 1-3. The solvents, photopolymerization initiators, and crosslinking agents used were as follows: Solvent: Propylene glycol monomethyl ether acetate (PGMEA) Photopolymerization initiator: Irgacure 369 (manufactured by BASF Co., Ltd.) Crosslinking agent: Pentaerythritol tetraacrylate (Tokyo Chemical Industry Co., Ltd.)

[0315] [Formation of Fluorine-Containing Resin Films 1-1 to 1-6 and Comparative Fluorine-Containing Resin Films 1-1 to 1-3] Each of the prepared fluorine-containing curable resin compositions 1-1 to 1-6 or comparative fluorine-containing curable resin compositions 1-1 to 1-3 was applied to a silicon wafer at a rotation speed of 1,000 rpm using a spin coater, and then heated on a hot plate at 90°C for 150 seconds to remove the solvent, thereby forming fluorine-containing resin films 1-1 to 1-6 or comparative fluorine-containing resin films 1-1 to 1-3, respectively, on the silicon wafer.

[0316] [Evaluation of fluorine-containing resin cured films using low-temperature curing method] Using a mask aligner (manufactured by SUSS MicroTec), the entire surface of the obtained resin film was irradiated with i-line light (wavelength 365 nm) without using a mask, and the exposure (200 mJ / cm 2 ) was carried out. For each film after exposure, (i) a method of forming a cured fluorine-containing resin film by curing at a high temperature (a method of heating at 230°C for 1 hour) was compared with the following methods (ii) to (iv) of forming a cured fluorine-containing resin film by curing at a low temperature. (ii): Heat at 90°C for 1 hour (iii): Using the mask aligner, the resin film is irradiated entirely with i-line light (wavelength 365 nm) without using a mask, and then subjected to additional exposure (2000 mJ / cm 2 ) and then heat at 90℃ for 1 hour (iv) Using a UV ozone treatment device (manufactured by Sen Special Light Sources Co., Ltd., model number: L17-110), the resin film is irradiated with UV ozone treatment for 5 minutes on the entire surface, and then heated at 90°C for 1 hour.

[0317] The fluorine-containing resin cured film was evaluated (degree of curing) by measuring the degree of change in contact angle with anisole, one of the solvents used in quantum dot color filters, 1 second and 10 seconds after a droplet was dropped. After measuring the thickness of the cured fluorine-containing resin film in advance, the silicon substrate having the cured film on its surface was immersed in anisole contained in a petri dish and heated on a hot plate at 140°C for 10 minutes. Thereafter, the anisole on the surface of the cured film was thoroughly removed with an air gun, and the film thickness was measured again. The cured film was evaluated based on the change in film thickness before and after immersion in anisole. The fluororesin cured film obtained by the method of (i) curing at high temperature was used as the standard value, and if it was confirmed that the evaluation result was comparable, it was judged as "good," and if not, it was judged as "bad." In other words, the smaller the change in contact angle with anisole over time, the better, and the smaller the change in film thickness before and after immersion in anisole, the better.

[0318] [Contact angle measurement] The contact angles of the fluororesin cured film surface and the comparative fluororesin cured film surface with methyl benzoate were measured using a contact angle meter DMs-601 manufactured by Kyowa Interface Science Co., Ltd.

[0319] [Film thickness measurement] The film thickness of the cured fluororesin film and the comparative cured fluororesin film was measured before and after immersion in anisole using a stylus surface profiler Dektak-8 manufactured by Bruker Nano. The results are shown in Table 1-3.

[0320] [Table 1-3]

[0321] As a result, the fluorine-containing resin cured films 1-1 to 1-6 formed by method (iv) showed results equivalent to those of the fluorine-containing resin cured film (reference value) formed by method (i), confirming that curing proceeded sufficiently even at low temperatures. Regarding the cured fluorine-containing resin films formed by method (ii) and by method (iii), good results were obtained for cured fluorine-containing resin films 1-2, 1-5 and 1-6. On the other hand, the comparative fluorine-containing resin cured films 1-1 to 1-3 showed a significant decrease in the change in contact angle with anisole over time and in the change in film thickness before and after immersion in anisole, compared with the fluorine-containing resin cured film (reference value) formed by the method (i), and were therefore poor. Furthermore, when the anisole after immersion in anisole was concentrated using an evaporator and the resulting oily substance was analyzed, each fluorine-containing resin was detected, confirming that it had dissolved in the anisole due to insufficient curing.

[0322] 5. Preparation of Photosensitive Resin Composition [Preparation of Photosensitive Resin Compositions 1-1 to 1-10 and Comparative Photosensitive Resin Compositions 1-1 to 1-6] Each of the produced fluororesins, each of the comparative fluororesins, a solvent, a photopolymerization initiator, a crosslinking agent, and an alkali-soluble resin were blended as shown in Table 1-4, and the resulting solutions were filtered through a 0.2 μm membrane filter to prepare photosensitive resin compositions 1 to 10 and comparative photosensitive resin compositions 1 to 6. The solvents, photopolymerization initiators, crosslinking agents, and alkali-soluble resins used were as follows: solvent; S-1: Propylene glycol monomethyl ether acetate (PGMEA), S-2: γ-butyrolactone, S-3: Propylene glycol monomethyl ether (PGME), S-4: Methyl ethyl ketone, S-5: Ethyl lactate Photoinitiators; Ini-1: 4-benzoylbenzoic acid, Ini-2: Irgacure 651 (manufactured by BASF Co., Ltd.), Ini-3: Irgacure 369 (manufactured by BASF Co., Ltd.) Crosslinking agents; CL-1: Pentaerythritol tetraacrylate (Tokyo Chemical Industry Co., Ltd.), CL-2: A-TMM-3 (Shin-Nakamura Chemical Co., Ltd.) Alkali-soluble resin; ASP-1: CCR-1235 (Nippon Kayaku Co., Ltd.) ASP-2: ZCR-1569H (Nippon Kayaku Co., Ltd.)

[0323] [Table 1-4]

[0324] 6. Low-temperature curing evaluation of each photosensitive resin composition Photosensitive resin compositions 1-1 to 1-10 and comparative photosensitive resin compositions 1-1 to 1-6 prepared in "5. Preparation of photosensitive resin compositions" were applied to silicon wafers at a rotation speed of 1,000 rpm using a spin coater in the same manner as in "4. Evaluation of low-temperature curing of each fluororesin film." Then, the wafers were heated on a hot plate at 90°C for 150 seconds to form photosensitive resin films 1-1 to 1-10 and comparative photosensitive resin films 1-1 to 1-6 (each number corresponds to the number of the photosensitive resin composition) on the silicon wafers.

[0325] [Evaluation of fluorine-containing resin cured films using low-temperature curing method] Using the mask aligner, the entire surface of the obtained resin film was irradiated with i-line (wavelength 365 nm) without using a mask, and exposure (200 mJ / cm 2 ) was carried out. For each film after exposure, a comparison was made between the fluorine-containing resin cured film formed by method (i) and the fluorine-containing resin cured films formed by methods (ii) to (iv), in the same manner as in "4. Evaluation of low-temperature curing of each fluorine-containing resin film." The evaluation of the fluororesin cured film (degree of progress of curing) was the same as in "4. Evaluation of low-temperature curing of each fluororesin film." The results are shown in Table 1-5.

[0326] [Table 1-5]

[0327] When the photosensitive resins 1-1 to 1-8 were cured by the method (iv), the same results were obtained as when they were cured by the method (i) of the reference example, and good cured films were obtained. On the other hand, when comparative fluorine-containing photocurable resins 1-1 to 1-3 were cured by method (iv), the results were inferior to those when cured by method (i). When photosensitive resins 1-1 to 1-8 were cured by methods (ii) and (iii), good results were obtained for photosensitive resins 1-3, 1-4, 1-9, and 1-10.

[0328] 7. Bank Evaluation Using the photosensitive resin compositions 1-1 to 1-10 and comparative photosensitive resin compositions 1-1 to 1-6 obtained in "5. Preparation of photosensitive resin compositions," banks 1-1 to 1-10 and comparative banks 1-1 to 1-6 were formed by the following method, and the bank performance was evaluated and compared.

[0329] [Bank formation] After cleaning a 10 cm square ITO substrate with ultrapure water and then acetone, the substrate was subjected to UV ozone treatment for 5 minutes using the aforementioned UV ozone treatment device. Next, the photosensitive resin compositions 1-1 to 1-10 and comparative photosensitive resin compositions 1-1 to 1-6 obtained in "5. Preparation of Photosensitive Resin Compositions" were applied to the resulting UV ozone-treated substrate using a spin coater at 1,000 rpm. The resulting substrate was then heated on a hot plate at 90°C for 150 seconds to form a 5 μm-thick fluorine-containing resin film and a comparative fluorine-containing resin film. Using a mask aligner (manufactured by SUSS MicroTec K.K.), the resulting resin film was exposed to i-line light (wavelength 365 nm) through a 5 μm line-and-space mask. The resulting film was immersed in an alkaline developer for 80 seconds and then washed with pure water for 60 seconds. Thereafter, the obtained patterned film was heated at 90°C for 1 hour (baking step), subjected to UV ozone treatment for 5 minutes, and then heated at 90°C for 1 hour. The resulting resin film was evaluated for developer solubility during the process, bank performance (sensitivity, resolution), and contact angle.

[0330] [Developer solubility] The exposed resin film on the ITO substrate was immersed in an alkaline developer at room temperature for 80 seconds to evaluate its solubility in the alkaline developer. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used as the alkaline developer. The solubility of the bank was evaluated by measuring the film thickness of the bank after immersion using a contact film thickness meter. The bank was rated as "soluble" when completely dissolved, and "insoluble" when the resist film remained undissolved. The results are shown in Table 1-6.

[0331] [Resist performance (sensitivity, resolution)] The optimum exposure dose Eop (mJ / cm) when forming the bank, which is the line and space pattern, is 2 ) was calculated and used as an index of sensitivity. The bank patterns thus obtained were observed under a microscope to evaluate the resolution, with the results being "excellent" when no line edge roughness was observed, "good" when slight roughness was observed, and "poor" when noticeable roughness was observed. The results are shown in Table 1-6.

[0332] [Contact angle] The contact angles of the banks and the comparative banks were measured over time for the entire surface of the substrate with the banks obtained through the above process. For the exposed areas where the residual film remains, a small change in the contact angle over time was considered good, while a low contact angle for the unexposed areas was considered good. The results are shown in Table 1-6.

[0333] [Table 1-6]

[0334] In the evaluation of developer solubility, each bank and each comparative bank were negative resists in which only the unexposed areas were dissolved, and in the evaluation of bank performance, they showed similar sensitivity, the 5 μm lines and spaces of the mask were transferred with good resolution, and the resolution was "excellent" with no line edge roughness observed. In other words, these evaluations showed that the fluorine-containing resin of the present disclosure and the comparative fluorine-containing resin had little effect on the bank. On the other hand, for each bank, the film heated at 90°C after UV ozone treatment showed no change in contact angle with anisole over time, and curing proceeded sufficiently even at low temperatures, making it an excellent bank with high liquid repellency.

[0335] (Second embodiment) The fluorine-containing resin according to the second embodiment of the present disclosure is characterized by containing both a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2).

[0336] [ka]

[0337] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 , R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (2-2), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3.

[0338] The molecular weight of the fluorine-containing resin is a weight-average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000. If the molecular weight is less than 1,000, the strength of the fluorine-containing resin film or bank for organic EL devices that is formed tends to decrease, while if the molecular weight is more than 1,000,000, the solubility in solvents is insufficient, making it difficult to form a fluorine-containing resin film by coating.

[0339] The dispersity (Mw / Mn) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, and particularly preferably from 1.01 to 3.00.

[0340] The fluororesin may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, but is preferably a random copolymer from the viewpoint of dispersing the respective properties appropriately rather than locally.

[0341] The fluorine-containing resin may be a polymer in which one or more types of units corresponding to the repeating unit of the above formula (2-1) are combined with one or more types of units corresponding to the repeating unit of the above formula (2-2). The fluorine-containing resin may also be a mixture (blend) of these polymers.

[0342] The fluorine content of the fluorine-containing resin is preferably 20% by mass or more and 80% by mass or less, based on 100% by mass of the fluorine-containing resin. If the fluorine content is within this range, the resin is easily dissolved in a solvent. When the fluorine-containing resin contains fluorine atoms, a fluorine-containing resin film or bank having excellent liquid repellency can be obtained.

[0343] Next, the repeating unit represented by formula (2-1) will be described. In formula (2-1), R 2-1represents a hydrogen atom, a fluorine atom or a methyl group, and is preferably a hydrogen atom or a methyl group.

[0344] In formula (2-1), R 2-2 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.

[0345] R 2-2 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.

[0346] In formula (2-1), R 2-3 , R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group.

[0347] R 2-3 , R 2-4are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, examples of which include 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, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred.

[0348] Among them, R 2-3 , R 2-4 are each independently 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.

[0349] As the repeating unit represented by formula (2-1), the following structures can be exemplified as preferred ones.

[0350] [ka]

[0351] [ka]

[0352] The content of the repeating unit represented by formula (2-1) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0353] If the content of the repeating unit of formula (2-1) is more than 70 mass%, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (2-1) is less than 5 mass%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0354] Depending on the application, a fluororesin film can also be formed by a method of applying pressure to the fluororesin as it is under heat without dissolving it in a solvent (hot pressing method), etc. In this case, even if more than 70 mass % of the repeating unit represented by formula (2-1) is used, the resistance of the fluororesin as a whole to UV ozone treatment or oxygen plasma treatment and the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment are not deteriorated, and such use is not prohibited in the present disclosure.

[0355] Here, the effects of the repeating unit represented by formula (2-1) according to the second embodiment of the present disclosure are not clear, but are presumed as follows: However, the effects of the fluorine-containing resin according to the second embodiment of the present disclosure are not limited to the effects described here.

[0356] The repeating unit represented by the formula (2-1) has the effect of imparting liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. 2-3 , R 2-4 When is a fluorine atom, a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched fluoroalkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms, this effect is particularly large and is therefore preferably used.

[0357] Furthermore, the repeating unit represented by the formula (2-1) has the effect of improving resistance to UV ozone treatment or oxygen plasma treatment, and the reason for this is thought to be as follows. In general, ester bonds are said to be susceptible to UV ozone treatment or oxygen plasma treatment and have low resistance (see also comparative fluororesin films 2-1 to 2-10 and Table 2-9 described later). Therefore, in a fluoropolymer consisting only of an acrylic moiety having an ester bond adjacent to the main chain, the ester bond serves as a reactive site, which is thought to be a factor in the low resistance of the fluoropolymer itself to the UV treatment (for example, the fluoropolymers described in Patent Documents 3 and 4).

[0358] In contrast, the repeating unit represented by the formula (2-1) according to the second embodiment of the present disclosure has a structure consisting of hydrocarbons that do not have a substituent that mainly contains oxygen, such as an ester bond, which is susceptible to UV ozone treatment or oxygen plasma treatment. Therefore, it is considered that the inclusion of the repeating unit represented by the formula (2-1) in a resin has the effect of improving the resistance of the fluorine-containing resin according to the second embodiment of the present disclosure to the treatment.

[0359] Next, the repeating unit represented by formula (2-2) will be described. In formula (2-2), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group.

[0360] In equation (2-2), W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

[0361] W 2 is —OC(═O)—NH—, this is one of the particularly preferred embodiments because the fluorine-containing resin according to the second embodiment of the present disclosure has better ink repellency after UV ozone treatment or oxygen plasma treatment.

[0362] In formula (2-2), A2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3.

[0363] Divalent linking group A 2 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.

[0364] Divalent linking group A 2 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.

[0365] Divalent linking group A 2 When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a 4-tert-butylcyclohexyl group.

[0366] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CHOH)CH-), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), a hydroxy-isobutylene group (-CHCH(CHOH)CH-), and a hydroxy-tert-butylene group (-C(CHOH)(CH)CH-).

[0367] Furthermore, when any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, examples of the substituted alkylene group include the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above, in which the hydroxyl groups are replaced with -OC(=O)-CH3.

[0368] Among them, the divalent linking group A 2 is preferably 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(CHOH)CH-), a 2-hydroxy-n-butylene group, or a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), more preferably an ethylene group, a propylene group, a 2-hydroxy-n-propylene group, or a hydroxy-isopropylene group (-CH(CHOH)CH-), and particularly preferably an ethylene group or a 2-hydroxy-n-propylene group.

[0369] In formula (2-2), Y 2 represents a divalent linking group, and represents -O- or -NH-, and more preferably -O-.

[0370] In formula (2-2), n represents an integer of 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are independently ortho, meta or para positions, and preferably para positions.

[0371] The repeating unit represented by formula (2-2) preferably has the following structure: Although the substitution position of the aromatic ring is exemplified as the para position, the substitution position may be independently the ortho position or the meta position.

[0372] [ka]

[0373] [ka]

[0374] [ka]

[0375] [ka]

[0376] The content of the repeating unit represented by formula (2-2) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0377] If the content of the repeating unit of formula (2-2) is more than 70 mass%, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (2-1) is less than 5 mass%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0378] Although the effects of the repeating unit represented by formula (2-2) according to the second embodiment of the present disclosure are not clear, it is presumed that the repeating unit has resistance to UV ozone treatment or oxygen plasma treatment. However, the effects of the fluorine-containing resin according to the second embodiment of the present disclosure are not limited to those described here.

[0379] As described above, the fluorine-containing resin according to the second embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (2-1) and a repeating unit represented by the formula (2-2) and another copolymer containing a repeating unit represented by the formula (2-1) and a repeating unit represented by the formula (2-2). In particular, the fluorine-containing resin according to the second embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (2-1) and a repeating unit represented by the formula (2-2). 2 a fluorine-containing resin containing a repeating unit represented by -OC(=O)-NH-; and W in formula (2-2) 2In one preferred aspect of the second embodiment of the present disclosure, the copolymer is a mixture with a fluorine-containing resin containing a repeating unit in which:

[0380] The fluorine-containing resin according to the second embodiment of the present disclosure preferably further contains a repeating unit represented by the following formula (2-3).

[0381] [ka]

[0382] In formula (2-3), R 2-7 represents a hydrogen atom or a methyl group.

[0383] In formula (2-3), R 2-8 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, and the fluorine content in the repeating unit is 30 mass% or more.

[0384] R 2-8 When 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.

[0385] The fluorine-containing resin according to the second embodiment of the present disclosure may be a polymer obtained by combining a repeating unit represented by formula (2-3), a repeating unit represented by formula (2-1), and a repeating unit represented by formula (2-2).

[0386] The fluorine-containing resin may also be a mixture (blend) of a polymer containing a repeating unit represented by formula (2-3) and a polymer containing a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2). In the case of a mixture, it may also be a mixture of a polymer containing a repeating unit represented by formula (2-3) and a repeating unit represented by formula (2-1) and a polymer containing a repeating unit represented by formula (2-2), or a mixture of a polymer containing a repeating unit represented by formula (2-3) and a repeating unit represented by formula (2-2) and a polymer containing a repeating unit represented by formula (2-1).

[0387] R 2-8 When is a linear hydrocarbon group, the repeating unit represented by the formula (2-3) is preferably a repeating unit represented by the following formula (2-3-1):

[0388] [ka] (In the formula, R 2-7 is R in equation (2-3). 2-7 X is a hydrogen atom or a fluorine atom. p is an integer of 1 to 4. q is an integer of 1 to 14. In the repeating unit represented by formula (2-3-1), it is particularly preferred that p is an integer of 1 to 2, q is an integer of 2 to 8, and X is a fluorine atom. As the repeating unit represented by formula (2-3), the following structures can be exemplified as preferred ones.

[0389] [ka]

[0390] [ka]

[0391] [ka]

[0392] [ka]

[0393] The content of the repeating unit represented by formula (2-3) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0394] If the content of the repeating unit of formula (2-3) is more than 70 mass %, the fluorine-containing resin tends to become less soluble in the solvent.

[0395] The repeating unit represented by formula (2-3) is a repeating unit that imparts liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. Therefore, when high liquid repellency to ink is desired, it is preferable that the fluorine-containing resin according to the second embodiment of the present disclosure contains a repeating unit represented by formula (2-3).

[0396] The fluorine-containing resin according to the second embodiment of the present disclosure preferably further contains a repeating unit represented by formula (2-4).

[0397] The fluorine-containing resin according to the second embodiment of the present disclosure may be a polymer obtained by combining a repeating unit represented by formula (2-4), a repeating unit represented by formula (2-1), and a repeating unit represented by formula (2-2). Alternatively, the fluorine-containing resin may be a polymer obtained by combining a repeating unit represented by formula (2-4), a repeating unit represented by formula (2-1), a repeating unit represented by formula (2-2), and a repeating unit represented by formula (2-3).

[0398] The fluorine-containing resin may also be a mixture (blend) of a polymer containing a repeating unit represented by formula (2-4) and a polymer containing a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2). In the case of a mixture, it may also be a mixture of a polymer containing a repeating unit represented by formula (2-4) and a repeating unit represented by formula (2-1) and a polymer containing a repeating unit represented by formula (2-2), or a mixture of a polymer containing a repeating unit represented by formula (2-4) and a repeating unit represented by formula (2-2) and a polymer containing a repeating unit represented by formula (2-1). Furthermore, when the fluorine-containing resin is a mixture containing a repeating unit represented by formula (2-3), it may also be a mixture that can be considered as a combination of the repeating units represented by formulas (2-1) to (2-4).

[0399] [ka]

[0400] In formula (2-4), R 2-9 represents a hydrogen atom or a methyl group.

[0401] In formula (2-4), B 2 are each independently a hydroxyl group, a carboxyl group, -C(=O)-OR 2-10 (R 2-10 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, and R 2-10 The fluorine content in the alkyl group is 30 mass % or more. 2-11 (R 2-11 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.

[0402] B 2 -C(=O)-OR 2-10 When R 2-10For specific examples, see R in formula (2-3). 2-8 The same can be mentioned here again.

[0403] B 2 -OC(=O)-R 2-11 When R 2-11 Examples of the alkyl group include 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 methyl group is more preferred.

[0404] In the formula (2-4), m represents an integer of 0 to 3.

[0405] As the repeating unit represented by formula (2-4), the following structures can be exemplified as preferred ones.

[0406] [ka]

[0407] [ka]

[0408] The content of the repeating unit represented by formula (2-4) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 20 to 40% by mass, relative to 100% by mass of the fluororesin.

[0409] If the content of the repeating unit of formula (2-4) is more than 70% by mass, the fluorine-containing resin tends to become less soluble in the solvent.

[0410] In formula (2-4), B 2is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (2-4) has solubility in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from the fluorine-containing resin, the fluorine-containing resin according to the second embodiment of the present disclosure may contain B 2 is a hydroxyl group or a carboxyl group. In particular, when it is desired to form a bank containing both the repeating unit represented by formula (2-1) and the repeating unit represented by formula (2-2A) in the second embodiment of the present disclosure, it is preferable to use a repeating unit represented by formula (2-4) in which B 2 Further containing a repeating unit represented by formula (2-4) in which is a hydroxyl group or a carboxyl group tends to improve the shape of the pattern film, which is one of the preferred embodiments.

[0411] In formula (2-4), B 2 is a hydroxyl group or a carboxyl group, the monomer corresponding to the repeating unit represented by formula (2-4) can also be used as a monomer of the repeating unit represented by formula (2-2) (formula (2-2a)) described later.

[0412] Among the fluorine-containing resins according to the second embodiment of the present disclosure, the following four embodiments can be mentioned as being particularly preferable.

[0413] <Aspect 2-1> A fluorine-containing resin containing both a repeating unit represented by the following formula (2-1) and a repeating unit represented by the following formula (2-2): Formula (2-1):R 2-1 and R 2-2 is a hydrogen atom, R 2-3 、 R 2-4 each independently represents a fluorine atom, a difluoromethyl group, or a trifluoromethyl group, Formula (2-2):R 2-5 and R 2-6 is a hydrogen atom, W 2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 2 is an ethylene group, Y 2 is -O-, n is 1

[0414] <Aspect 2-2> A fluorine-containing resin containing both a repeating unit represented by the following formula (2-1) and a repeating unit represented by the following formula (2-2): Formula (2-1): Same as embodiment 2-1 Formula (2-2):R 2-5 and R 2-6 is a hydrogen atom, W 2 -O-, A 2 is a 2-hydroxy-n-propylene group or a hydroxy-isopropylene group (-CH(CHOH)CH-), Y 2 is -O-, n is 1

[0415] <Aspect 2-3> Fluorine-containing resins containing repeating units represented by the following formulas (2-1), (2-2) and (2-3-1): Formula (2-1): Same as embodiment 2-1 Formula (2-2): Same as embodiment 2-1 Formula (2-3-1):R 2-7 is a methyl group, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom

[0416] <Aspect 2-4> Fluorine-containing resins containing repeating units represented by the following formulas (2-1), (2-2), (2-3-1) and (2-4): Formula (2-1): Same as embodiment 2-1 Formula (2-2): Same as embodiment 2-1 Formula (2-3-1): Same as aspect 2-1 Formula (2-4):R 2-9 is a hydrogen atom, B 2 is a hydroxyl group or a carboxyl group, m is 1

[0417] The fluorine-containing resin according to the second embodiment of the present disclosure can be easily produced through two steps, by polymerizing monomers represented by formula (2-1a) and formula (2-2a) to obtain a fluorine-containing resin precursor containing repeating units represented by formula (2-1) and formula (2-2b), and then subjecting formula (2-2b) in the repeating units represented by formula (2-1) and formula (2-2b) to an addition reaction or condensation reaction with an acrylic acid derivative represented by formula (2-2c).

[0418] [ka] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 , R 2-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. R in formula (2-1a) 2-1 , R 2-2 , R 2-3 and R 2-4 is R in formula (2-1). 2-1 , R 2-2 , R 2-3 and R 2-4 are synonymous with each other. In formula (2-2), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3. In formula (2-2a), R 2-5 and n is R in formula (2-2). 2-5 and n respectively. D 2 represents a hydroxyl group or a carboxyl group. R in formula (2-2b) 2-5 , n and D 2 is R in formula (2-2) 2-5 , n and D in formula (2-2a) 2 are synonymous with each other. R in formula (2-2c) 2-6 , A 2 and Y 2 is R in formula (2-2) 2-6 , A 2 and Y 2 are synonymous with each other. Z 2 represents an isocyanate group (-N=C=O), an acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group), an acid anhydride, a halogen atom, a hydroxyl group, an amino group (-NH), or an oxirane group.

[0419] In formula (2-2), formula (2-2a), formula (2-2b) and formula (2-2c), the substitution positions of the aromatic rings are each independently ortho-, meta- or para-positions.

[0420] Each step will be explained below. [First step] The first step is a step of polymerizing the monomers represented by formula (2-1a) and formula (2-2a) to produce a fluorine-containing resin precursor containing repeating units represented by formula (2-1) and formula (2-2b).

[0421] [ka]

[0422] The monomer represented by formula (2-1a) may be a commercially available product and used as is, or may be prepared by a known method or a method similar thereto. For example, it is preferable to prepare it by the method described in Journal of Organic Chemistry, 1970, Vol. 35, No. 6, pp. 2096-2099, or a method similar thereto.

[0423] The repeating unit represented by formula (2-1) is formed by cleavage of the polymerizable double bond of the monomer represented by formula (2-1a). In the polymerization reaction, no change occurs in the structure other than the polymerizable double bond, and the original structure is maintained. Therefore, in the monomer represented by formula (2-1a), R 2-1 , R 2-2 , R 2-3 and R 2-4 In the repeating unit represented by formula (2-1), R 2-1 , R 2-2 , R 2-3 and R 2-4 and the like, and specific substituents can be the same as those exemplified in the description of the repeating unit represented by formula (2-1). Furthermore, preferred structures of the monomer represented by formula (2-1a) can be the same as those of the corresponding monomers before cleavage of the polymerizable double bond in the repeating units exemplified in the description of the repeating unit represented by formula (2-1).

[0424] The monomer represented by formula (2-2a) may be a commercially available product and used as it is, or may be prepared by a known method or a method similar thereto. It is preferable to use a commercially available product because it is easily available.

[0425] The repeating unit represented by formula (2-2b) is formed by cleavage of the polymerizable double bond of the monomer represented by formula (2-2a). In the polymerization reaction, no changes occur in the structure other than the polymerizable double bond, and the original structure is maintained.

[0426] In the monomer represented by formula (2-2a), R 2-5 is preferably a hydrogen atom and n is preferably 1. That is, R 2-5 is a hydrogen atom, D 2 is a hydroxyl group and n is 1, or R 2-5 is a hydrogen atom, D 2 is a carboxyl group and n is 1. The polymerization method of the monomers represented by formula (2-1a) and formula (2-2a) will be described.

[0427] The polymerization method is not particularly limited as long as it is a commonly used method, but radical polymerization and ionic polymerization are preferred, and in some cases, coordination anionic polymerization, living anionic polymerization, cationic polymerization, ring-opening metathesis polymerization, vinylene polymerization, vinyl addition, etc. can also be used. Among these, radical polymerization is particularly preferred. Well-known methods can be applied as each polymerization method. Below, a radical polymerization method will be described, but other methods can also be easily polymerized according to well-known literature, etc.

[0428] The radical polymerization may be carried out in the presence of a radical polymerization initiator or a radical initiation source by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, in a batch, semi-continuous, or continuous operation.

[0429] The radical polymerization initiator is not particularly limited, but examples include azo compounds, peroxide compounds, persulfate compounds, and redox compounds. In particular, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), tert-butyl peroxypivalate, di-tert-butyl peroxide, isobutyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, tert-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, ammonium persulfate, and the like are preferred.

[0430] The reaction vessel used for the polymerization reaction is not particularly limited. In addition to the monomer and initiator, a polymerization solvent is preferably used in the polymerization reaction. The polymerization solvent is preferably one that does not inhibit radical polymerization. Typical examples include esters such as ethyl acetate and n-butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; hydrocarbons such as toluene and cyclohexane; and alcohols such as methanol, isopropyl alcohol, and ethylene glycol monomethyl ether. Solvents such as water, linear ethers, cyclic ethers, fluorocarbons, and aromatic solvents can also be used. The polymerization solvent can be used alone or in combination. A molecular weight modifier such as mercaptan can also be used. The reaction temperature for the polymerization reaction varies depending on the radical polymerization initiator or radical polymerization initiation source. It is generally preferred that the temperature be 20°C to 200°C, more preferably 30°C to 140°C, and particularly preferably 50°C to 120°C.

[0431] The polymerization time is usually 0.1 to 48 hours, preferably 1 to 24 hours, but it is preferable to use analytical equipment such as high performance liquid chromatography (HPLC) or nuclear magnetic resonance (NMR) to determine the end point of the polymerization when the monomer is consumed. After the polymerization is completed, the reaction can be stopped by cooling the polymerization solution to below room temperature.

[0432] The monomer concentration at the start of polymerization relative to 100% by mass of the polymerization reaction system is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. If the monomer concentration is lower than this range, the reaction rate of the polymerization reaction tends to decrease, and if the concentration is higher than this range, the viscosity of the polymerization liquid tends to increase.

[0433] Methods for removing the organic solvent or water from the obtained solution or dispersion of the fluororesin precursor include reprecipitation, filtration, distillation by heating under reduced pressure, etc. The obtained fluororesin precursor may be further purified by, for example, washing with a solvent in which the fluororesin is insoluble during filtration.

[0434] [Second process] The second step is a step of producing a fluorine-containing resin containing repeating units represented by formula (2-1) and formula (2-2) by subjecting the repeating units represented by formula (2-1) and formula (2-2b) in the repeating units represented by formula (2-2b) to an addition reaction or condensation reaction with an acrylic acid derivative represented by formula (2-2c).

[0435] [ka]

[0436] The acrylic acid derivative represented by formula (2-2c) may be a commercially available product and used as is, or may be prepared by a known method or a method similar thereto. It is preferable to use a commercially available product because it is easily available.

[0437] R in formula (2-2c) 2-6 , A 2 and Y 2 is R in formula (2-2) 2-6 , A 2 and Y 2 Specific substituents are the same as those R listed in the explanation of the repeating unit represented by formula (2-2). 2-6 , A 2 and Y 2 can again be mentioned here.

[0438] Z 2 represents an isocyanate group (-N=C=O), acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group), acid anhydride, halogen atom, hydroxyl group or a hydroxyl group protected by a protecting group, amino group (-NH2), or oxirane group.

[0439] Z 2 Examples of the acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group) in the formula (I) include acid fluorides such as -C(=O)-F, -C(=O)-Cl, -C(=O)-Br, and -C(=O)-I, and groups in which -C(=O)- and a 2-imidazolyl group are linked together.

[0440] Z 2 Examples of the acid anhydride in the formula include -C(=O)-OC(=O)-CH3, -C(=O)-OC(=O)-(tert-butyl), -C(=O)-OC(=O)-CF3, and the like.

[0441] Z 2 Examples of the hydroxyl group protected by a protecting group in the formula (I) include a hydroxyl group protected by a protecting group such as a methanesulfonyl group, a trifluoromethanesulfonyl group, or a p-toluenesulfonyl group.

[0442] Z 2 Examples of the oxirane group in Z include an ethylene oxide group, a 1,2-propylene oxide group, and a 1,3-propylene oxide group. 2 Particularly preferred are an isocyanate group, —C(═O)—Cl, and an ethylene oxide group.

[0443] As the acrylic acid derivative represented by formula (2-2c), the following structures can be exemplified as preferred examples.

[0444] [ka]

[0445] [ka]

[0446] This reaction is represented by D in formula (2-2b). 2 and Z in formula (2-2c) 2 Although the mode of reaction varies depending on the type of the compound, any mode of reaction can be carried out using a general addition reaction or condensation reaction method. Three modes of reaction are exemplified below.

[0447] Aspect (2-1): D in formula (2-2b) 2 is a hydroxyl group, and Z in formula (2-2c) 2 When is an isocyanate group, W in the resulting formula (2-2) 2 can form the bond "-OC(=O)-NH-".

[0448] Aspect (2-2): D in formula (2-2b) 2 is a carboxyl group, and Z in formula (2-2c) 2 When is an isocyanate group, W in the resulting formula (2-2) 2 can undergo decarboxylation in the system to form a bond that becomes "-C(=O)-NH-", or a bond that does not undergo decarboxylation in the system to form a bond that becomes "-C(=O)-OC(=O)-NH-".

[0449] Aspect (2-3): C in formula (2-2b) is a hydroxyl group, and Z in formula (2-2c) 2 is an ethylene oxide group, W in the resulting formula (2-2) 2 can form a bond that results in "-O-".

[0450] The production method of the second step will be described below. Regardless of which of the above embodiments is employed, the following method can usually be employed.

[0451] The amount of the acrylic acid derivative represented by formula (2-2c) used to react with the repeating units represented by formula (2-1) and formula (2-2b) is not particularly limited, but is usually 0.01 to 5 mol, preferably 0.05 to 3 mol, and more preferably 0.05 to 1 mol, per 1 mol of the repeating units represented by formula (2-1) and formula (2-2b). It is particularly preferred that the amount of the acrylic acid derivative used is 0.2 to 1 mol.

[0452] The reaction is usually carried out in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, tetrahydrofuran, acetonitrile, propylene glycol monomethyl monoacetate (PGMEA), N,N-dimethylformamide, etc. These solvents may be used alone or in combination of two or more. The reaction temperature is not particularly limited and is usually in the range of −20 to +100° C., preferably 0 to +80° C., and more preferably +10 to +40° C. The reaction is preferably carried out with stirring.

[0453] The reaction time depends on the reaction temperature, but is usually from several minutes to 100 hours, preferably from 30 minutes to 50 hours, and more preferably from 1 to 20 hours. It is preferable to use an analytical instrument such as a nuclear magnetic resonance spectrometer (NMR) and determine the end point of the reaction when the acrylic acid derivative represented by general formula (2-2c) is consumed.

[0454] In this reaction, a base may be used as a catalyst. Preferred examples of the base catalyst include organic bases such as trimethylamine, triethylamine, tripropylamine, tributylamine, and diisopropylethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of such a base catalyst used is not particularly limited, but is 0.01 to 5 mol, preferably 0.02 to 3 mol, and more preferably 0.05 to 1 mol, per 1 mol of the repeating units represented by formula (2-1) and formula (2-2b).

[0455] After the reaction is completed, a fluororesin containing both the repeating unit represented by formula (2-1) and the repeating unit represented by formula (2-2) can be obtained by ordinary means such as reprecipitation, filtration, extraction, crystallization, recrystallization, etc. The obtained fluororesin may be further purified, and a method in which the fluororesin is washed by pouring it over during filtration using a solvent in which the fluororesin is insoluble can be used.

[0456] The photosensitive resin composition according to the second embodiment of the present disclosure contains at least the above-described fluorine-containing resin, a solvent, and a photopolymerization initiator.

[0457] The photosensitive resin composition according to the second embodiment of the present disclosure is particularly suitable as a negative resin composition for obtaining a fluorine-containing resin film or a bank for organic EL devices, which will be described later.

[0458] The solvent in the photosensitive resin composition according to the second embodiment of the present disclosure is not particularly limited as long as it dissolves the fluorine-containing resin, and examples thereof include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, fluorine-containing solvents, etc. These may be used alone or in combination of two or more.

[0459] Specific examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. Specific 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.

[0460] Specific 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), and the monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0461] Specific examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0462] Specific 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.

[0463] Examples of aromatic solvents include xylene and toluene.

[0464] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0465] 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.

[0466] Among them, the solvents are 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 The solvent is preferably at least one selected from the group consisting of propylene glycol 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. Methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone are more preferred.

[0467] The amount of solvent in the photosensitive resin composition according to the second embodiment of the present disclosure is usually in the range of 50% by mass or more and 2,000% by mass or less relative to 100% by mass of the fluorine-containing resin concentration (however, when the photosensitive resin composition contains an alkali-soluble resin described below, the combined concentration of the resin is used). It is preferably 100% by mass or more and 1,000% by mass or less. By adjusting the amount of solvent, the thickness of the resin film to be formed can be adjusted, and within the above range, a resin film thickness particularly suitable for obtaining a bank for organic electroluminescence can be obtained.

[0468] The photopolymerization initiator in the photosensitive resin composition according to the second embodiment of the present disclosure is not particularly limited as long as it polymerizes, by electromagnetic waves or electron beams, the monomer having a polymerizable double bond mentioned in the description of the production method for the fluorine-containing resin, and any known photopolymerization initiator can be used.

[0469] As the photopolymerization initiator, a photoradical initiator or a photoacid initiator can be used, and these may be used alone, or a photoradical initiator and a photoacid initiator may be used in combination, or two or more types of photoradical initiators or photoacid initiators may be mixed and used. Furthermore, by using an additive together with the photopolymerization initiator, it is also possible to carry out living polymerization in some cases, and known additives can be used as the additive.

[0470] Photoradical initiators can be specifically classified into intramolecular cleavage types in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction types in which radicals are generated in combination with a hydrogen donor such as a tertiary amine or ether, and either type may be used. Photoradical initiators other than those types listed above may also be used.

[0471] Specific examples of the photoradical initiator include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based initiators.

[0472] Specific examples of benzophenone-based compounds 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.

[0473] Specific examples of acetophenone-based compounds 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.

[0474] Specific examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylformate, and 9,10-phenanthrenequinone, among which 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0475] Specific examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0476] Specific examples of quinones include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0477] Specific examples of acyloin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Of these, benzoin and benzoin methyl ether are preferred.

[0478] As the photoradical initiator, benzophenone-based, acetophenone-based and diketone-based initiators are preferred, and benzophenone-based initiators are more preferred.

[0479] Among commercially available photoradical initiators, preferred ones include the following product names manufactured by BASF Co., Ltd.: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Lugacure 907, Irgacure 2959, Irgacure OXE-01, Darocur 1173, Lucilin TPO, etc. Among these, Irgacure 651 and Irgacure 369 are more preferred.

[0480] Specifically, the photoacid initiator is an onium salt consisting of a pair of at least one cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, and (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate.

[0481] Among these, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0482] Examples of commercially available photoacid generators include those manufactured by San-Apro Co., Ltd. under the product names CPI-100P, CPI-110P, CPI-101A, CPI-200K, and CPI-210S; those manufactured by Dow Chemical Japan under the product names Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, and Cyracure Photocuring Initiator UVI-6976; and those manufactured by ADEKA Corporation under the product names ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, and ADEKA Optomer SP -172, Adeka Optomer SP-300, Nippon Soda Co., Ltd. product names: CI-5102, CI-2855, Sanshin Chemical Industry Co., Ltd. product names: San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110, San-Aid SI-180, Lamberti product names: Esacure 1064, Esacure 1187, and Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 250.

[0483] The content of the photopolymerization initiator in the photosensitive resin composition according to the second embodiment of the present disclosure is 0.1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 20% by mass or less, relative to 100% by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains an alkali-soluble resin described below, the concentration of the resin combined). If the content of the photopolymerization initiator is less than 0.1% by mass, the crosslinking effect tends to be insufficient, and if it exceeds 30% by mass, the resolution and sensitivity tend to decrease.

[0484] The photosensitive resin composition according to the second embodiment of the present disclosure preferably contains (a) a crosslinking agent and (b) an alkali-soluble resin in addition to the fluorine-containing resin according to the second embodiment of the present disclosure, which are essential components, the solvent, and the photopolymerization initiator. Furthermore, if necessary, (c) a naphthoquinone diazide group-containing compound, (d) a basic compound, (e) other additives, etc. may be contained.

[0485] (a) Crosslinking agent The crosslinking agent reacts with the repeating unit represented by formula (2-2) to allow the resin to adopt a crosslinked structure, thereby improving the mechanical strength of the film that is formed.

[0486] Known crosslinking agents can be used, and specific examples include compounds in which an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, propyleneurea, or glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol, and the hydrogen atoms of the amino group are substituted with hydroxymethyl groups or lower alkoxymethyl groups, polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyfunctional isocyanate compounds, and polyfunctional acrylate compounds. Here, those using melamine are called melamine-based crosslinking agents, those using urea are called urea-based crosslinking agents, those using alkylene ureas such as ethyleneurea and propyleneurea are called alkylene urea-based crosslinking agents, and those using glycoluril are called glycoluril-based crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.

[0487] The crosslinking agent is preferably at least one selected from these crosslinking agents, and glycoluril-based crosslinking agents and polyfunctional acrylate compounds are particularly preferred.

[0488] Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine, with hexamethoxymethylmelamine being preferred.

[0489] Examples of the urea-based crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among these, bismethoxymethylurea is preferred.

[0490] Examples of alkylene urea-based crosslinking agents include ethylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0491] Examples of glycoluril crosslinking agents include mono-, di-, tri-, and / or tetrahydroxymethylated glycoluril, mono-, di-, tri-, and / or tetramethoxymethylated glycoluril, mono-, di-, tri-, and / or tetraethoxymethylated glycoluril, mono-, di-, tri-, and / or tetrapropoxymethylated glycoluril, and mono-, di-, tri-, and / or tetrabutoxymethylated glycoluril.

[0492] Examples of the polyfunctional acrylate compound include polyfunctional acrylates (for example, product names A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol diacrylates (for example, product names A-200, A-400, and A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.), urethane acrylates (for example, product names UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, and UA-7200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and pentaerythritol tetraacrylate. Preferred examples of the polyfunctional acrylate compound are shown below.

[0493] [ka]

[0494] [ka]

[0495] [ka]

[0496] The content of the crosslinking agent in the photosensitive resin composition according to the second embodiment of the present disclosure is 10% by mass or more and 300% by mass or less, and preferably 50% by mass or more and 200% by mass or less, relative to 100% by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains an alkali-soluble resin described below, the concentration of the resin combined). If the content of the crosslinking agent is less than 10% by mass, the crosslinking effect tends to be insufficient, and if it exceeds 300% by mass, the resolution and sensitivity tend to decrease.

[0497] (b) Alkali-soluble resin The alkali-soluble resin is one of the preferred embodiments because it has the effect of improving the shape of the bank obtained from the photosensitive resin composition according to the second embodiment of the present disclosure.

[0498] The alkali-soluble resin may be an alkali-soluble novolak resin, which can be obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst.

[0499] 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-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more.

[0500] 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.

[0501] Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, etc. These acid catalysts may be used alone or in combination of two or more.

[0502] Other examples of alkali-soluble resins include acid-modified epoxy acrylates. Commercially available acid-modified epoxy acrylates 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.

[0503] The weight average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive resin composition.

[0504] The content of the alkali-soluble resin in the photosensitive resin composition according to the second embodiment of the present disclosure is 500% by mass or more and 10,000% by mass or less, and preferably 1,000% by mass or more and 7,000% by mass or less, relative to 100% by mass of the fluororesin. If the content of the alkali-soluble resin exceeds 10,000% by mass, the ink repellency of the fluororesin according to the second embodiment of the present disclosure after UV ozone treatment or oxygen plasma treatment tends to be insufficient.

[0505] (c) Naphthoquinone diazide group-containing compound The naphthoquinone diazide group-containing compound is not particularly limited, and any compound commonly used as a photosensitive component in i-line resist compositions can be used. The naphthoquinone diazide group-containing compound is one of the preferred embodiments because it has the effect of improving the shape of the bank obtained from the photosensitive resin composition according to the second embodiment of the present disclosure.

[0506] Specific examples of naphthoquinone diazide group-containing compounds include naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds, naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid ester compounds, and orthoanthraquinone diazide sulfonic acid ester compounds. Among these, naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, and naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds are preferred due to their excellent solubility. These compounds may be used alone or in combination of two or more.

[0507] The content of the naphthoquinone diazide group-containing compound in the photosensitive resin composition according to the second embodiment of the present disclosure is usually 10% by mass to 60% by mass, and preferably 20% by mass to 50% by mass, relative to 100% by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains the alkali-soluble resin, the concentration of the resin is the total). If the content exceeds 60% by mass, it tends to be difficult to obtain the sensitivity required for the photosensitive resin.

[0508] (d) Basic compounds The basic compound has the function of slowing down the diffusion rate of the acid generated by the photoacid generator when it diffuses into the film, and the incorporation of the basic compound is expected to have the effect of adjusting the acid diffusion distance to improve the shape of the bank and to improve the stability of providing a bank shape with the desired precision even if the waiting time before exposure after bank formation is long.

[0509] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, and specific examples include secondary or tertiary aliphatic amines and alkyl alcohol amines. These basic compounds may be used alone or in combination of two or more.

[0510] Examples of aliphatic amines include alkylamines or alkyl alcoholamines in which at least one hydrogen atom of ammonia (NH3) has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, and di-n-octylamine. Examples of suitable alkylamines include n-nonylamine, di-n-decanylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decanylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, and alkyl alcoholamines are more preferred. Among alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0511] Examples of aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; heterocyclic amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, and 4,4-dimethylimidazoline; ,6-pentamethyl-4-piperidyl) sebagate and other hindered amines; 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine and other alcoholic nitrogen-containing compounds; picoline, lutidine, pyrrole, piperidine, piperazine, indole, hexamethylenetetramine and the like.

[0512] In the photosensitive resin composition according to the second embodiment of the present disclosure, the content of the basic compound is usually 0.001% by mass to 2% by mass, and preferably 0.01% by mass to 1% by mass, relative to 100% by mass of the fluorine-containing resin (however, when the photosensitive resin composition contains the alkali-soluble resin, the concentration of the resin is the total). If the amount of the basic compound is less than 0.001% by mass, it becomes difficult to obtain a sufficient effect as an additive, and if it exceeds 2% by mass, resolution and sensitivity tend to decrease.

[0513] (e) Other additives The photosensitive resin composition according to the second embodiment of the present disclosure may contain other additives as needed. Known additives may be used as appropriate, and examples of such additives include dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion agents, and antioxidants.

[0514] The surfactant preferably contains either a fluorine-based or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom), or two or more of these surfactants.

[0515] The fluorine-containing resin film according to the second embodiment of the present disclosure contains both a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2A). That is, the fluorine-containing resin film according to the second embodiment of the present disclosure is obtained by curing the above-mentioned photosensitive resin composition.

[0516] [ka] [In formula (2-1), R 2-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2-2 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. R 2-3 、 R 2-4each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 2-1 , R 2-3 , R 2-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (2-2A), R 2-5 , R 2-6 each independently represents a hydrogen atom or a methyl group. W 2 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 2 represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with hydroxyl groups or -OC(=O)-CH3. Y 2 represents a divalent linking group, and represents -O- or -NH-. n represents an integer of 1 to 3.

[0517] As for the preferred structure of the repeating unit represented by formula (2-1), those mentioned in the description of the repeating unit represented by formula (2-1) above can be mentioned again here.

[0518] The repeating unit represented by formula (2-2A) is formed by cleavage of the polymerizable double bond of the repeating unit represented by formula (2-2). In the polymerization reaction, no change occurs in the structure other than the polymerizable double bond, and the original structure is maintained. Therefore, in the repeating unit represented by formula (2-2A), R 2-5 , R 2-6 , W 2 , A 2 , Y 2 and n is R in the repeating unit represented by formula (2-2).2-5 , R 2-6 , W 2 , A 2 , Y 2 and n are synonymous with each other, and specific substituents can be the same as those exemplified for the repeating unit represented by formula (2-2) above. Furthermore, preferred structures for the repeating unit represented by formula (2-2A) can be the same as those exemplified for the repeating unit represented by formula (2-2) above, except that the repeating unit is formed by cleavage of the polymerizable double bond in the preferred structures exemplified in the description of the repeating unit represented by formula (2-2).

[0519] The fluorine-containing resin film according to the second embodiment of the present disclosure can be suitably used as a simple film without a pattern, or as a film with a pattern, i.e., a bank as described below. In this specification, the term "fluorine-containing resin film" refers to a film without a pattern.

[0520] The fluorine-containing resin film according to the second embodiment of the present disclosure has excellent water and oil repellency due to its low surface free energy, and can be used as a film for protecting substrates in a variety of applications, such as a water and oil repellent agent for treating fabrics (substrates) for clothing and the like, or a sealing agent for protecting microfabricated semiconductor substrates (substrates).

[0521] When forming a fluorine-containing resin film, the composition of the photosensitive resin composition described above preferably contains the essential components of a fluorine-containing resin, a solvent, and a photopolymerization initiator, and further contains a crosslinking agent. Other additives may be contained as necessary. Examples of the solvent, photopolymerization initiator, crosslinking agent, and other additives are the same as those listed above in the description of the photosensitive resin composition.

[0522] When it is desired to pursue performance other than the liquid repellency against ink after UV ozone treatment or oxygen plasma treatment that the fluorine-containing resin according to the second embodiment of the present disclosure has, it is possible to incorporate the properties of other resins by mixing (blending) the resin with other resins.

[0523] The type of monomer for such "other resins" is not particularly limited, but examples include styrene compounds, acrylic acid esters, methacrylic acid esters, etc. These may be homopolymers of one type or copolymers of two or more types. Among these, fluorine-free monomers are preferably used.

[0524] When a fluororesin film is formed by mixing with "other resins" in this way, the mass % of the fluororesin according to the second embodiment of the present disclosure relative to 100 mass % of the fluororesin film is usually 50 mass % to 99 mass %, more preferably 60 mass % to 99 mass %, and particularly preferably 70 mass % to 99 mass %. The remainder is "other resins" or the above-mentioned "various additives," etc. If the composition of the fluororesin according to the second embodiment of the present disclosure is less than 50 mass %, the ink repellency after UV ozone treatment or oxygen plasma treatment tends to decrease.

[0525] When forming a fluorine-containing resin film, the concentration of the fluorine-containing resin relative to 100% by mass of the photosensitive resin composition is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less, from the viewpoint of ease of application and ease of film formation.

[0526] The method for forming a film using the photosensitive resin composition according to the second embodiment of the present disclosure can employ techniques similar to conventionally known coating methods, and a suitable method can be selected depending on the object to be coated. For example, the fluororesin according to the second embodiment of the present disclosure can be preferably applied using an appropriate coating device such as a slit coater, die coater, gravure coater, dip coater, or spin coater. Other methods, such as dip coating, spray coating, and roller coating, can also be used.

[0527] It is preferable that the solvent contained in the photosensitive resin composition is not left in the fluororesin film after the fluororesin film is applied to the substrate and dried.

[0528] The substrate after coating with the fluorine-containing resin film can be heated at 80°C or higher and 300°C or lower to remove the solvent. Heating is preferably carried out until no weight loss of the fluorine-containing resin film is observed. Heating may be carried out under atmospheric pressure, under pressure, or under reduced pressure. Furthermore, heating may be carried out in the air, in an inert atmosphere, or while flowing a predetermined gas.

[0529] If the heating temperature is less than 80°C, the solvent is likely to remain, and if it exceeds 300°C, the fluororesin tends to decompose. If the heating temperature is 100°C or higher and 250°C or lower, the solvent can be removed without causing decomposition of the fluororesin, which is more preferable.

[0530] The object to be coated may be a microfabricated semiconductor substrate or fabric such as clothing.

[0531] Here, the fluorine-containing resin film formed on the substrate may be formed on the entire surface of the substrate, or may be formed on only a part of the substrate.

[0532] The thickness of the obtained fluorine-containing resin film is preferably 1 μm or more and 500 μm or less. If the fluorine-containing resin film is thinner than 1 μm, the mechanical strength of the film may decrease, and if the thickness exceeds 500 μm, the surface irregularities become large, making it difficult to obtain a flat film.

[0533] The bank according to the second embodiment of the present disclosure contains both the repeating unit represented by formula (2-1) and the repeating unit represented by formula (2-2A). That is, the bank according to the second embodiment of the present disclosure is obtained by curing the above-described photosensitive resin composition.

[0534] When forming the bank according to the second embodiment of the present disclosure, the photosensitive resin composition preferably contains the essential components of a fluorine-containing resin, a solvent, and a photopolymerization initiator, and further contains a crosslinking agent and an alkali-soluble resin. If necessary, the composition may further contain (c) a naphthoquinone diazide group-containing compound, (d) a basic compound, and (e) other additives. The respective components mentioned in the description of the photosensitive resin composition above can be mentioned again here.

[0535] As a method for forming the bank according to the second embodiment of the present disclosure, a resist pattern forming method using conventional photoresist technology can be adopted. The bank forming method will be described below.

[0536] The banks can be formed through the following steps: a film-forming step (2-4-1) in which the photosensitive resin composition is applied to a substrate to form a film; an exposure step (2-4-2) in which the photomask pattern is transferred to the film by irradiating it with electromagnetic waves or electron beams through a photomask; a development step (2-4-3) in which the film is developed using a developer to obtain the banks; and a UV ozone treatment or oxygen plasma treatment step (2-4-4) in which residual organic matter in the bank recesses is removed. A heating step (2-4-5) may then be added as necessary. Each step will be explained below using an example.

[0537] 2-4-1. Film forming process The film-forming process involves applying the photosensitive resin composition to a substrate such as a silicon wafer by spin coating or the like, and then heating the silicon wafer on a hot plate to remove the solvent, thereby forming a film on the substrate. Heating to remove the solvent is typically performed at a temperature of 60°C to 200°C for 10 seconds to 10 minutes, preferably at a temperature of 80°C to 150°C for 30 seconds to 2 minutes.

[0538] The substrate used may be a silicon wafer, metal, glass, ITO substrate, or the like. An organic or inorganic film may be pre-formed on the substrate. For example, an anti-reflective film or a multilayer resist underlayer may be present, and a pattern may be formed on the underlayer. The substrate may also be pre-washed. For example, it can be washed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), or the like.

[0539] 2-4-2. Exposure process The exposure step is a step in which a desired photomask is set in an exposure device, and the film is irradiated with electromagnetic waves or electron beams through the photomask, followed by heating on a hot plate.

[0540] The wavelength of the electromagnetic waves or electron beams used for exposure is preferably 100 to 600 nm, more preferably 300 to 500 nm, and particularly preferably includes i-line (365 nm), h-line (405 nm), and g-line (436 nm). If necessary, light of 330 nm or less may be cut off.

[0541] Examples of light sources include KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), and F2 excimer laser light (wavelength 157 nm).

[0542] The exposure dose of electromagnetic waves or electron beams is 1 mJ / cm 2 More than 200mJ / cm 2 Less than or equal to 10 mJ / cm 2 More than 100mJ / cm 2 The following is the result.

[0543] Heating after exposure is carried out on a hot plate, usually at a temperature of 60°C or higher and 150°C or lower for 10 seconds to 5 minutes, preferably at a temperature of 80°C or higher and 130°C or lower for 30 seconds to 3 minutes.

[0544] 2-4-3.Developing process The development step is a step in which a developer is used to dissolve either the exposed portion of the film or the unexposed portion of the film in the exposure step described above, thereby forming a bank.

[0545] The developer may be, for example, an aqueous alkali solution such as an aqueous tetramethylammonium hydroxide (TMAH) solution or an aqueous tetrabutylammonium hydroxide (TBAH) solution, or an organic solvent such as propylene glycol monomethyl ether acetate (PGMEA) or butyl acetate.

[0546] The concentration of the tetramethylammonium hydroxide (TMAH) aqueous solution is usually 0.1% by mass or more and 5% by mass or less, and preferably 2% by mass or more and 3% by mass or less. As the developing method, a known method can be used, for example, a dipping method, a puddle method, a spray method, or the like.

[0547] The development time (the time during which the developer is in contact with the film) is usually from 10 seconds to 3 minutes, and preferably from 30 seconds to 2 minutes.

[0548] After development, if necessary, a step of washing the formed banks with deionized water, etc. The washing method and washing time can be the same as those for the developing method and developing time using the developer.

[0549] The developed film is heated on a hot plate to crosslink and remove low-boiling components, typically at a temperature of 60°C to 300°C for 10 seconds to 120 minutes, preferably at a temperature of 140°C to 250°C for 10 minutes to 90 minutes.

[0550] 2-4-4.UV ozone treatment or oxygen plasma treatment process The UV ozone treatment or oxygen plasma treatment step is a step in which the entire surface of the substrate having the obtained banks is irradiated with UV ozone or oxygen plasma to remove organic matter remaining in the bank recesses.

[0551] The duration of the UV ozone treatment is usually from 10 seconds to 30 minutes, preferably from 1 minute to 15 minutes.

[0552] The duration of the oxygen plasma treatment is usually from 10 seconds to 30 minutes, preferably from 1 minute to 15 minutes.

[0553] If the UV ozone treatment or oxygen plasma treatment time is less than 10 seconds, the remaining organic matter tends to be incompletely removed, and if it exceeds 30 minutes, the film thickness of the pattern film tends to decrease.

[0554] 2-4-5.Heating process After the UV ozone treatment or oxygen plasma treatment step, a step of heating the substrate having the resulting banks may be carried out as necessary, which can improve the liquid repellency of the upper surfaces of the banks according to the second embodiment of the present disclosure.

[0555] Heating is carried out on a hot plate, typically at a temperature of 60°C or higher and 300°C or lower for a time of 10 seconds to 30-120 minutes, preferably at a temperature of 140°C or higher and 250°C or lower for a time of 10 minutes to 1590 minutes.

[0556] When the bank according to the second embodiment of the present disclosure contains a repeating unit represented by formula (2-4) in which B is a carboxyl group, the heat treatment step is preferably carried out, which is one of the aspects in which the bank can be improved in terms of its liquid repellency, particularly with respect to ink, by the heat treatment step.

[0557] A display element according to a second embodiment of the present disclosure includes the bank. Examples of the display element according to the second embodiment of the present disclosure include an organic electroluminescence display (hereinafter referred to as an organic EL display), a micro LED display, and a quantum dot display.

[0558] (Example according to the second embodiment) Hereinafter, the aspects of the second embodiment of the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these embodiments.

[0559] 1. Synthesis of Monomer [Synthesis Example 2-1] Synthesis of 1,1-bis(trifluoromethyl)butadiene (BTFBE) 400 g of concentrated sulfuric acid was added to a 1000 ml glass flask equipped with a stirrer, and after heating to 100 °C, 300 g of 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol (product of Central Glass Co., Ltd.) was gradually added dropwise over 1 hour. After completion of the dropwise addition, stirring was carried out at 100 °C for 60 minutes, and the reaction solution was 19 analyzed by F-NMR, and no residual raw material was detected. Next, a fraction with a boiling point of 68 - 70 °C was recovered from the reaction solution by atmospheric distillation, and 1,1-bis(trifluoromethyl)butadiene (hereinafter referred to as BTFBE) was obtained in a yield of 58%.

[0560] [Chemical Formula]

[0561] [NMR Analysis Results] 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 5.95 (1H, dd) 6.05 (1H, dd), 6.85 (1H, m), 7.04 (1H, m) 19 F-NMR (solvent: deuterated chloroform, reference substance: C6D6); δ (ppm) -65.3 (3F, m), -58.4 (3F, m)

[0562] [Synthesis Example 2-2] Synthesis of 4-hydroxystyrene (p-HO-St) (Synthesized by referring to the examples of JP-A-2016-98181.) In a 1000 ml glass flask equipped with a stirrer, 100 g of 4-acetoxystyrene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St) and 300 g of methanol were mixed at room temperature (approximately 20°C), and 0.50 g of 1,3,5-trihydroxybenzene (equivalent to 0.5 mass% of p-AcO-St) was added as a polymerization inhibitor. Next, this solution was cooled to 0°C in an ice bath, and then a 12 mass% aqueous sodium hydroxide solution (equivalent to 1.0 equivalent of p-AcO-St) was gradually added dropwise over 40 minutes, followed by stirring at 0°C for 30 minutes. The reaction solution was 1 Analysis by H-NMR revealed that no residual raw materials were detected. Next, an 18% by mass aqueous hydrochloric acid solution (equivalent to 0.8 equivalents of p-AcO-St) was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes after the addition. The pH of this solution was measured and found to be 6. The resulting reaction solution was extracted with 360 g of methyl t-butyl ether at room temperature (approximately 20°C). It was then washed twice with 330 g of purified water. 1,3,5-trihydroxybenzene was added to the resulting organic layer in an amount equivalent to 1% by mass of 4-hydroxystyrene. The 4-hydroxystyrene was then concentrated to 72% by mass and poured into n-octane, a poor solvent, cooled to 0°C. The solution was then immersed in an ice bath and stirred for 1 hour to precipitate 4-hydroxystyrene crystals. The crystals were filtered and further washed with n-octane. The crystals were then dried under reduced pressure at 25°C to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield: 66%).

[0563] [ka]

[0564] 2. Production of Fluorine-Containing Resin (First Step: Polymerization) [Measurement of the molar ratio of each repeating unit] NMR The molar ratio of each repeating unit in the polymer is 1 H-NMR, 19 F-NMR, or 13 It was determined from C-NMR measurements.

[0565] [Measurement of Molecular Weight of Polymer] GPC The weight-average molecular weight Mw and molecular weight distribution (the 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). One ALPHA-M column and one ALPHA-2500 column (both are products of Tosoh Corporation) were connected in series, and measurement was carried out using tetrahydrofuran (THF) as the eluent. A differential refractive index detector was used as the detector.

[0566] 2-1. Polymerization of Fluorine-containing Resin Precursor [Polymerization of Fluorine-containing Resin Precursor 2-1] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 9.5 g (0.05 mol) of BTFBE obtained in Synthesis Example 1, 12.2 g (0.1 mol) of p-HO-St obtained in Synthesis Example 2, 43.2 g (0.1 mol) of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 65 g of MEK were taken, and 1.6 g (0.005 mol) of 2,2'-azobis(2-methylbutyronitrile) (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) was added. After degassing while stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 75 °C and reacted for 6 hours. When 350 g of n-heptane was dropped into the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. Vacuum drying was carried out at 60 °C to obtain 58 g of fluorine-containing resin precursor 2-1 as a transparent viscous substance with a yield of 90%.

[0567] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2-1, expressed in mol%, was repeating unit by BTFBE: repeating unit by p-HO-St: repeating unit by MA-C6F = 21:51:28.

[0568] [Chemical Structure]

[0569] <GPC measurement result> Mw = 12,000, Mw / Mn = 1.4

[0570] [Polymerization of fluorine-containing resin precursor 2-2] A fluorine-containing resin precursor 2-2 containing the following repeating units was obtained in a yield of 87% by the same procedure as the synthesis of the fluorine-containing resin precursor 2-1, except that vinyl benzoic acid (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as VBA) was used instead of p-HO-St.

[0571] <NMR measurement result> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2-2, expressed in mol%, was: repeating unit by BTFBE: repeating unit by VBA: repeating unit by MA-C6F = 16:57:27.

[0572] [Chemical formula]

[0573] <GPC measurement result> Mw = 9,000, Mw / Mn = 1.4

[0574] [Polymerization of fluorine-containing resin precursor 2-3] At room temperature (about 20 °C) in a 300 ml glass flask equipped with a stirrer, 9.5 g (0.05 mol) of BTFBE, 6.1 g (0.05 mol) of p-HO-St, 7.4 g (0.05 mol) of VBA, 43.2 g (0.1 mol) of MA-C6F, and 65 g of MEK were taken, 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and heated to 75 °C and reacted for 6 hours. When 350 g of n-heptane was dropped into the reaction system, a white solid precipitated. After filtering and separating this solid, vacuum drying was carried out at 60 °C to obtain 59 g of a fluorine-containing resin precursor 2-3 as a white solid in a yield of 89%.

[0575] <NMR measurement result> The composition ratio of each repeating unit of the fluororesin precursor 2-3 was, expressed in mol%, repeating unit by BTFBE: repeating unit by p-HO-St: repeating unit by VBA: repeating unit by MA-C6F = 15:25:25:35.

[0576]

Chemical formula

[0577] <GPC measurement results> Mw = 7,500, Mw / Mn = 1.3

[0578] [Polymerization of fluororesin precursor 2-4] A fluororesin precursor 2-4 containing the following repeating units was obtained in a yield of 86% by the same procedure as the synthesis of the fluororesin precursor 2-3, except that styrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as St) was used instead of p-HO-St.

[0579] <NMR measurement results> The composition ratio of each repeating unit of the fluororesin precursor 2-4 was, expressed in mol%, repeating unit by BTFBE: repeating unit by VBA: repeating unit by MA-C6F: repeating unit by St = 16:26:34:24.

[0580]

Chemical formula

[0581] <GPC measurement results> Mw = 7,300, Mw / Mn = 1.3

[0582] [Polymerization of fluororesin precursor 2-5] A fluororesin precursor 2-5 containing the following repeating units was obtained in a yield of 84% by the same procedure as the synthesis of the fluororesin precursor 2-3, except that St was used instead of VBA.

[0583] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2-5, expressed in mol%, was the repeating unit by BTFBE: the repeating unit by p-HO-St: the repeating unit by MA-C6F: the repeating unit by St = 16:25:35:25.

[0584]

Chemical formula

[0585] <GPC measurement results> Mw = 6,900, Mw / Mn = 1.3

[0586] [Polymerization of fluorine-containing resin precursor 2-6] A fluorine-containing resin precursor 2-6 containing the following repeating units was obtained in a yield of 88% by the same procedure as the synthesis of the fluorine-containing resin precursor 2-3, except that p-AcO-St was used instead of VBA.

[0587] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2-6, expressed in mol%, was the repeating unit by BTFBE: the repeating unit by p-HO-St: the repeating unit by MA-C6F: the repeating unit by p-AcO-St = 17:23:33:27.

[0588]

Chemical formula

[0589] <GPC measurement results> Mw = 7,900, Mw / Mn = 1.4

[0590] 2-2. Polymerization of comparative fluorine-containing resin precursor [Polymerization of comparative fluorine-containing resin precursor 2-1] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 17.32 g (0.2 mol) of methacrylic acid (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MAA), 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of hexafluoroisopropyl methacrylate (product of Central Glass Co., Ltd., hereinafter referred to as HFIP-M), 84 g of MEK were taken, 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and after heating to 80 °C, the reaction was carried out for 6 hours. The reaction solution after the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 55 g of a fluorine-containing resin precursor 2-1 as a white solid with a yield of 64%.

[0591] <NMR measurement results> The composition ratio of each repeating unit of the comparative fluorine-containing resin precursor 2-1, expressed in mol ratio, was repeating unit by MA-C6F: repeating unit by HFIP-M: repeating unit by MAA = 20:26:54.

[0592]

Chemical formula

[0593] <GPC measurement results> Mw = 9,700, Mw / Mn = 1.5

[0594] [Polymerization of comparative fluorine-containing resin precursor 2-2] In a 300 ml glass flask equipped with a stirrer, at room temperature, 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of HFIP-M, 8.66 g (0.1 mol) of MAA, 13.01 g (0.1 mol) of 2-hydroxyethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HEMA), 88 g of MEK were taken, 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, heated to 80 °C, and then reacted for 6 hours. The reaction solution after the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 60 g of a fluorine-containing resin precursor 2-2 as a white solid with a yield of 68%.

[0595] <NMR measurement results> The composition ratio of each repeating unit of the comparative fluorine-containing resin precursor 2-2, expressed in mol ratio, was: repeating unit by MA-C6F: repeating unit by HFIP-M: repeating unit by MAA: repeating unit by HEMA = 24:26:26:24.

[0596]

Chemical formula

[0597] <GPC measurement results> Mw = 10,700, Mw / Mn = 1.5

[0598] [Polymerization of comparative fluorine-containing resin precursor 2-3] In a 300 ml glass flask equipped with a stirrer, at room temperature, 12.2 g (0.10 mol) of p-HO-St, 43.2 g (0.1 mol) of MA-C6F, 55 g of MEK were taken, 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, heated to 80 °C, and then reacted for 6 hours. The reaction solution after the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 45 g of a comparative fluorine-containing resin precursor 2-3 as a white solid with a yield of 81%.

[0599] <NMR measurement results> The composition ratio of each repeating unit of Comparative Fluorine-containing Resin Precursor 2-3, expressed in molar ratio, was: repeating unit by p-HO-St : repeating unit by MA-C6F = 55:45.

[0600]

Chemical formula

[0601] <GPC measurement results> Mw = 15,700, Mw / Mn = 1.7

[0602] [Polymerization of Comparative Fluorine-containing Resin Precursor 2-4] [[ID=2,4]]Except for using VBA instead of p-HO-St, Comparative Fluorine-containing Resin Precursor 2-4 containing the following repeating units was obtained in a yield of 88% by the same procedure as the synthesis of Comparative Fluorine-containing Resin Precursor 2-3.

[0603] <NMR measurement results> The composition ratio of each repeating unit of Comparative Fluorine-containing Resin Precursor 2-4, expressed in molar ratio, was: repeating unit by VBA : repeating unit by MA-C6F = 57:43.

[0604]

Chemical formula

[0605] <GPC measurement results> Mw = 16,300, Mw / Mn = 1.7

[0606] Table 2-1 shows the repeating units contained in the obtained Fluorine-containing Resin Precursors 2-1 to 2-6, Comparative Fluorine-containing Resin Precursors 2-1 to 2-4, their molar ratios, weight-average molecular weights (Mw), molecular weight distributions (Mw / Mn), and yields.

[0607]

Table 2-1

[0608] 3. Production of Fluorine-Containing Resin (Second Step: Addition Reaction or Condensation Reaction) Fluorine-containing resins were synthesized by reacting fluororesin precursors 2-1 to 2-6 or comparative fluororesin precursors 2-1 to 2-4 obtained in "2. Production of fluororesin (first step: polymerization)" with an acrylic acid derivative. Karenz-AOI, Karenz-BEI (products of Showa Denko K.K.), or glycidyl acrylate (product of Tokyo Chemical Industry Co., Ltd.) was used as the acrylic acid derivative. This reaction is an addition reaction or condensation reaction between the hydroxyl group or hydroxyl group of the carboxylic acid moiety in each fluororesin precursor and the acrylic acid derivative.

[0609] Examples of the synthesis of each fluororesin are described below, and the names of the obtained fluororesins are as follows: The first number represents the number of the fluororesin precursor, and the following alphabet represents the acrylic acid derivative used, with "A" representing the use of Karenz-AOI, "B" representing the use of Karenz-BEI, and "G" representing the use of glycidyl acrylate, and the final number in parentheses represents the nominal amount (molar ratio) of the acrylic acid derivative introduced relative to each resin precursor.

[0610] [ka]

[0611] [Synthesis of Fluorine-Containing Resin 2-1-A(50)] In a 300 ml glass flask equipped with a stirrer, 130 g of fluororesin precursor 2-1 (hydroxyl equivalent: 0.270 mol) and 260 g of PGMEA were placed, and 19 g (0.135 mol) of Karenz-AOI and 5.32 g (0.0528 mol) of triethylamine were added and reacted at room temperature for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 1500 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40 °C, yielding 140 g of fluororesin 2-1-A (50) as a white solid in a 94% yield.

[0612] <NMR Measurement Results> In the fluororesin 2-1-A(50), the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz-AOI and the amount of remaining hydroxyl groups (unreacted rate), expressed in molar ratio, were 57:43. Also, it was confirmed that the composition ratio of each repeating unit that does not react with the crosslinking group site (the repeating unit by BTFBE and the repeating unit by MA-C6F) did not change from the used fluororesin precursor 2-1 (the same as before crosslinking group introduction). Also, the newly formed bond (W in formula (2-2)) 2 ) was “-O-C(=O)-NH-”.

[0613] [Synthesis of Fluororesin 2-1-A(100)] A fluororesin 2-1-A(100) containing the following repeating units was obtained in a yield of 96% by the same procedure as the synthesis of fluororesin 2-1-A(50) except that 38 g (0.270 mol) of Karenz-AOI was used.

[0614] <NMR Measurement Results> In the fluororesin 2-1-A(100), the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz-AOI and the amount of remaining hydroxyl groups (unreacted rate), expressed in molar ratio, were 95:5. Also, it was confirmed that the composition ratio of each repeating unit that does not react with the crosslinking group site (the repeating unit by BTFBE and the repeating unit by MA-C6F) did not change from the used fluororesin precursor 2-1 (the same as before crosslinking group introduction). Also, the newly formed bond (W in formula (2-2)) 2 ) was “-O-C(=O)-NH-”.

[0615] [Synthesis of Fluororesin 2-1-B(50)] A fluororesin 2-1-B(50) containing the following repeating units was obtained in a yield of 93% by the same procedure as the synthesis of fluororesin 2-1-A(50) except that 32 g (0.134 mol) of Karenz-BEI was used instead of Karenz-AOI.

[0616] <NMR Measurement Results> In the fluororesin 2-1-B(50), the amount of acrylic acid derivative introduced (reaction rate) and the amount of remaining hydroxyl groups (unreacted rate) derived from Karenz-BEI were 53:47 in terms of mol ratio. Also, it was confirmed that the composition ratio of each repeating unit that does not react with the crosslinking group site (the repeating unit by BTFBE and the repeating unit by MA-C6F) did not change from the used fluororesin precursor 2-1 (the same as before crosslinking group introduction). Further, the newly formed bond (W in formula (2-2)) 2 ) was “-O-C(=O)-NH-”.

[0617] [Synthesis of fluororesin 2-1-G(50)] Into a 300 ml glass flask equipped with a stirrer, 130 g of fluororesin precursor 2-1 (hydroxyl group equivalent 0.270 mol) and 260 g of PGMEA were taken, 17 g (0.132 mol) of glycidyl acrylate was added, and the reaction was carried out at 80 °C for 18 hours. After the reaction was completed, the content was concentrated, 1500 g of heptane was added, and precipitation was caused. This precipitate was filtered off and dried under reduced pressure at 40 °C to obtain 135 g of fluororesin 2-1-G(50) as a white solid with a yield of 92%.

[0618] <NMR measurement results> In the fluororesin 2-1-G, the amount of acrylic acid derivative introduced (reaction rate) and the amount of remaining hydroxyl groups (unreacted rate) derived from glycidyl acrylate were 55:45 in terms of mol ratio. Also, it was confirmed that the composition ratio of each repeating unit that does not react with the crosslinking group site (the repeating unit by BTFBE and the repeating unit by MA-C6F) did not change from the used fluororesin precursor 2-1 (the same as before crosslinking group introduction). Further, the newly formed bond (W in formula (2-2)) 2 ) was “-O-”.

[0619] [Synthesis of fluororesin 2-2-A(10)] Into a 300 ml glass flask equipped with a stirrer, 130 g (hydroxyl equivalent: 0.355 mol) of the fluororesin precursor 2-2, 300 g of PGMEA were taken, 10 g (0.071 mol) of Karenz-AOI was added, and the mixture was reacted at 60 °C for 18 hours. After the reaction, the reaction solution was concentrated, 1500 g of n-heptane was added, and precipitation was induced. This precipitate was separated by filtration and dried under reduced pressure at 40 °C to obtain 132 g of fluororesin 2-2-A(10) as a white solid with a yield of 94%.

[0620] <NMR measurement results> In the fluororesin 2-2-A(10), the amount of acrylic acid derivative introduced (reaction rate) and the amount of remaining hydroxyl groups (unreacted rate) derived from Karenz-AOI were 10:90 in terms of molar ratio. Also, it was confirmed that the composition ratio of each repeating unit (the repeating unit by BTFBE and the repeating unit by MA-C6F) that does not react with the crosslinking group site did not change from the used fluororesin precursor 2-1 (the same as before the introduction of the crosslinking group). Further, the newly formed bond (W in formula (2-2)) was “-C(=O)-NH-”. [[ID=--7]] 2 ) was “-C(=O)-NH-”.

[0621] [Synthesis of fluororesins 2-2-B(5) to 2-6-G(50)] Similar to the fluororesins 2-1-A(50), 2-1-A(100), 2-1-G(50), or 2-2-A(10), the fluororesins 2-2-B(5) to 2-6-G(50) were produced. The used fluororesin precursors, acrylic acid derivatives, formed crosslinking group structures (W in the above formula (2-2)), crosslinking group introduction amounts (reaction rates), and remaining hydroxyl group amounts (unreacted rates) are shown in Table 2-2. 2 ) are shown in Table 2-2.

[0622] [Synthesis of comparative fluororesins 2-1-A(50) to 2-4-G(50)] Similar to the fluororesins 2-1-A(50), 2-1-A(100), 2-1-G(50), or 2-2-A(10), the comparative fluororesins 2-1-A(50) to 2-4-G(50) were produced. The used comparative fluororesin precursors, types of introduced crosslinking group sites, crosslinking group introduction amounts (reaction rates), and remaining hydroxyl group amounts (unreacted rates) are shown in Table 2-3.

[0623] [Table 2-2]

[0624] [Table 2-3]

[0625] 4. Preparation of Photosensitive Resin Composition [Preparation of Photosensitive Resin Compositions 2-1 to 2-38 and Comparative Photosensitive Resin Compositions 2-1 to 2-12] The produced fluorine-containing resins, comparative fluorine-containing resins, solvents, photopolymerization initiators, crosslinking agents, alkali-soluble resins, naphthoquinone diazide group-containing compounds, or basic compounds were mixed as shown in Tables 2-4 to 2-6, and the resulting solutions were filtered through a 0.2 μm membrane filter to prepare photosensitive resin compositions 2-1 to 2-38 and comparative photosensitive resin compositions 2-1 to 2-12. In the tables, unadded components are indicated by "-".

[0626] The solvents, photopolymerization initiators, crosslinking agents, alkali-soluble resins, naphthoquinone diazide group-containing compounds, or basic compounds used were as follows: solvent; S-1: propylene glycol monomethyl ether acetate (PGMEA), S-2: γ-butyrolactone, S-3: propylene glycol monomethyl ether (PGME), S-4: methyl ethyl ketone, S-5: cyclohexanone, S-6: ethyl lactate, S-7: butyl acetate Photoinitiators; Ini-1: 4-benzoylbenzoic acid, Ini-2: Irgacure 651 (product of BASF Co., Ltd.), Ini-3: Irgacure 369 (product of BASF Co., Ltd.) Crosslinking agents; CL-1: Pentaerythritol tetraacrylate (Tokyo Chemical Industry Co., Ltd. product), CL-2: A-TMM-3 (Shin-Nakamura Chemical Co., Ltd. product) Alkali-soluble resin; ASP-1: CCR-1235 (Nippon Kayaku Co., Ltd. product) Naphthoquinone diazide group-containing compounds; N-1: Naphthoquinone-1,2-diazide-5-sulfonic acid ester compound (Toyo Gosei Co., Ltd., PC-5) Basic compounds; B-1: Triethanolamine (product of Tokyo Chemical Industry Co., Ltd.)

[0627] [Table 2-4]

[0628] [Table 2-5]

[0629] [Table 2-6]

[0630] 5. Evaluation of resistance and liquid repellency of fluororesin film against UV ozone treatment [Formation of Fluorine-Containing Resin Films 2-1 to 2-38 and Comparative Fluorine-Containing Resin Films 2-1 to 2-12] The prepared photosensitive resin compositions 2-1 to 2-38 and comparative photosensitive resin compositions 2-1 to 2-12 were applied to silicon wafers at a rotation speed of 1,000 rpm using a spin coater, and then heated on a hot plate at 100°C for 150 seconds to form fluorine-containing resin films 2-1 to 2-38 and comparative fluorine-containing resin films 2-1 to 2-12 (each number corresponds to the number of the photosensitive resin composition) on the silicon wafers, respectively. Using the obtained fluorine-containing resin films 2-2, 2-10, 2-16, 2-22, 2-28, and 2-34 and the comparative fluorine-containing resin films 2-1, 2-4, 2-7, and 2-10, the contact angles to water, anisole, and methyl benzoate were measured before and after UV ozone treatment, and after heating. Water, anisole, and methyl benzoate are used as ink solvents.

[0631] [UV ozone treatment process and heating process] The fluorine-containing resin film on the silicon wafer and the comparative fluorine-containing resin film were treated with UV ozone for 10 minutes using a UV ozone treatment device, model PL17-110, manufactured by Sen Special Light Sources Co., Ltd., followed by heating at 230°C for 60 seconds.

[0632] [Contact angle measurement] Using a contact angle meter DMs-601 manufactured by Kyowa Interface Science Co., Ltd., the contact angles of the fluorine-containing resin film and the comparative fluorine-containing resin film surfaces to water, anisole, and methyl benzoate were measured before and after the UV ozone treatment and after the subsequent heating step.

[0633] [Film thickness measurement] Using a stylus surface profiler Dektak-8 manufactured by Bruker Nano, the film thickness of the fluorine-containing resin film and the comparative fluorine-containing resin film was measured before and after the UV ozone treatment and after the subsequent heating step.

[0634] [Measurement of molecular weight change] Before and after UV ozone treatment, and after the subsequent heating step, the fluorine-containing resin film and the comparative fluorine-containing resin film were scraped off from the silicon wafer with a spatula, and the obtained solid was dissolved in THF and subjected to molecular weight measurement by GPC. When multiple peaks were detected, the results of each molecular weight were shown in the table, and when multiple peaks were detected and the molecular weight was 1,000 or less, the result was shown as "≦1000, multiple."

[0635] Table 2-7 shows the contact angle results for each step, and Table 2-8 shows the film thickness measurement results and molecular weight results for each step.

[0636] [Table 2-7]

[0637] [Table 2-8]

[0638] From the results in Table 2-7, it was confirmed that the fluorine-containing resin films 2-2, 2-10, 2-16, 2-22, 2-28, and 2-34 according to the second embodiment of the present disclosure showed a decrease in contact angle after UV ozone treatment, but the subsequent heat treatment step improved the contact angle to approximately the same as that before UV ozone treatment, demonstrating that the fluorine-containing resin films after UV ozone treatment exhibited good liquid repellency. On the other hand, the comparative fluorine-containing resin films 2-1, 2-4, 2-7, and 2-10 showed a high contact angle before UV ozone treatment, but the contact angle decreased after UV ozone treatment and remained low even after the subsequent heat treatment, demonstrating that the liquid repellency after UV ozone treatment was insufficient.

[0639] The results in Table 2-8 show that the fluorine-containing resin films 2-2, 2-10, 2-16, 2-22, 2-28, and 2-34 according to the second embodiment of the present disclosure showed a slight decrease in film thickness after UV ozone treatment, but the molecular weight of the remaining film was roughly the same, indicating that they had excellent resistance to UV ozone treatment.On the other hand, the comparative fluorine-containing resin films 2-1, 2-4, 2-7, and 2-10 showed a significant decrease in film thickness after UV ozone treatment, and the molecular weight of the remaining film was also significantly reduced compared to before UV ozone treatment, indicating that they had insufficient resistance to UV ozone treatment.

[0640] 6. Evaluation of liquid repellency on the top surface of the bank after UV ozone treatment or oxygen plasma treatment Photosensitive resin compositions 2-2, 2-6, 2-8, 2-10, 2-14, 2-16, and 2-26 obtained in "4. Preparation of Photosensitive Resin Compositions" and comparative photosensitive resin compositions 2-1, 2-4, 2-7, and 2-12 were used to form banks 2-2, 2-6, 2-8, 2-10, 2-14, 2-16, and 2-26, and comparative banks 2-1, 2-4, 2-7, and 2-12, and the bank performance was evaluated and compared. The results are shown in Table 2-9 below. For performance comparison, the components of the photosensitive resin compositions used in this experiment were the same except for the fluorine-containing resin or comparative fluorine-containing resin.

[0641] [Bank formation] After washing a 10 cm square ITO substrate with ultrapure water and then with acetone, the substrate was subjected to UV ozone treatment for 5 minutes using the aforementioned UV ozone treatment device. Next, using photosensitive resin compositions 2-2, 2-6, 2-8, 2-10, 2-14, 2-16, and 2-26 obtained in "4. Preparation of photosensitive resin compositions" and comparative photosensitive resin compositions 2-1, 2-4, 2-7, and 2-12, the substrates after the UV ozone treatment were coated at a rotation speed of 1,000 rpm using a spin coater, and heated on a hot plate at 100°C for 150 seconds to form fluorine-containing resin films and comparative fluorine-containing resin films with a thickness of 2 μm. Using a mask aligner (product of SUSS MicroTec KK), the obtained resin film was exposed to i-line light (wavelength 365 nm) through a mask with a line and space of 5 μm. The resulting exposed resin film was evaluated for developer solubility, bank performance (sensitivity, resolution), and contact angle.

[0642] [Developer solubility] The exposed resin film on the ITO substrate was immersed in an alkaline developer at room temperature for 80 seconds to evaluate its solubility in the alkaline developer. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used as the alkaline developer. The solubility of the bank was evaluated by measuring the film thickness of the bank after immersion using a contact film thickness meter. The bank was rated as "soluble" when completely dissolved, and "insoluble" when the resist film remained undissolved.

[0643] [Bank performance (sensitivity, resolution)] The optimum exposure dose Eop (mJ / cm) when forming the bank, which is the line and space pattern, is 2 ) was calculated and used as an index of sensitivity. The bank patterns were also observed under a scanning electron microscope to evaluate their resolution. Those with no visible line edge roughness were rated "excellent," those with slight visible line edge roughness were rated "good," and those with significant line edge roughness were rated "poor."

[0644] [Contact angle] The substrate with the bank obtained by the above process was heated at 230°C for 60 minutes, and then the entire substrate was subjected to UV ozone treatment or oxygen plasma treatment for 10 minutes. It was then heated at 230°C for 60 seconds. The contact angles of the bank and comparative bank surfaces with anisole were measured before and after the UV ozone treatment or oxygen plasma treatment, and after the subsequent heating step. The UV ozone treatment device and contact angle meter used were the same as those described above. The oxygen plasma treatment device used was a plasma dry cleaner PDC210 manufactured by Yamato Scientific Co., Ltd., and oxygen plasma treatment was performed under the conditions of an oxygen gas flow rate of 30 cc / min and an output of 300 W.

[0645] [Table 2-9]

[0646] As shown in Table 2-9, in the evaluation of developer solubility, both the bank according to the second embodiment of the present disclosure and the comparative bank were negative resists in which only the unexposed areas were dissolved, and in the evaluation of bank performance, they showed similar sensitivity, the 5 μm lines and spaces of the mask were transferred with good resolution, and the resolution was "excellent" with no visible line edge roughness. In other words, these evaluations showed that the fluorine-containing resin according to the second embodiment of the present disclosure and the comparative fluorine-containing resin had little effect on the bank.

[0647] On the other hand, in the bank according to the second embodiment of the present disclosure, the contact angle of the exposed area (corresponding to the upper surface of the bank) to anisole decreased after UV ozone treatment or oxygen plasma treatment, but improved after the subsequent heating step, demonstrating good liquid repellency.In the comparative bank, the contact angle decreased after UV ozone treatment or oxygen plasma treatment, and remained low with almost no change even after the subsequent heating step, indicating insufficient liquid repellency.

[0648] (Third embodiment) The third embodiment of the present disclosure will be described below in the following order. 3-1. Fluorine-containing resin 3-1-1. Repeating unit represented by formula (3-1) 3-1-2. Repeating unit represented by formula (3-2) 3-1-3. Repeating unit represented by formula (3-3) 3-1-4. Repeating unit represented by formula (3-4) 3-1-5. Repeating unit represented by formula (3-5) 3-1-6.Preferred embodiments of fluorine-containing resin 3-1-7. Manufacturing method of fluorine-containing resin 3-2. Photosensitive resin composition 3-3. Fluorine-containing resin membrane 3-4. Bank 3-5. Display element

[0649] 3-1. Fluorine-containing resin The fluorine-containing resin according to the third embodiment of the present disclosure is characterized by containing both a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). [ka]

[0650] [In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 3-2 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. R 3-3 , R 3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group. In formula (3-2), R 3-5 , R 3-6each independently represents a hydrogen atom or a methyl group. W 3 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 3-1 , A 3-2 represents a divalent linking group, each independently representing 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. Y 3-1 , Y 3-2 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1.

[0651] The molecular weight of the fluorine-containing resin is a weight-average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000. If the molecular weight is less than 1,000, the strength of the fluorine-containing resin film or bank for organic EL devices that is formed tends to decrease, while if the molecular weight is more than 1,000,000, the solubility in solvents is insufficient, making it difficult to form a fluorine-containing resin film by coating.

[0652] The dispersity (Mw / Mn) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, and particularly preferably from 1.01 to 3.00.

[0653] The fluororesin may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, but is preferably a random copolymer from the viewpoint of dispersing the respective properties appropriately rather than locally.

[0654] The fluorine-containing resin may be a polymer in which one or more types of units corresponding to the repeating unit of the formula (3-1) described below are combined with one or more types of units corresponding to the repeating unit of the formula (3-2) described below. The fluorine-containing resin may also be a mixture (blend) of these polymers.

[0655] The fluorine content of the fluorine-containing resin is preferably 20% by mass or more and 80% by mass or less, based on 100% by mass of the fluorine-containing resin. If the fluorine content is within this range, the resin is easily dissolved in a solvent. When the fluorine-containing resin contains fluorine atoms, a fluorine-containing resin film or bank having excellent liquid repellency can be obtained.

[0656] 3-1-1. Repeating unit represented by formula (3-1) Next, the repeating unit represented by formula (3-1) will be described.

[0657] In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group, and is preferably a hydrogen atom or a methyl group.

[0658] In formula (3-1), R 3-2 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.

[0659] R 3-2 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.

[0660] In formula (3-1), R 3-3 、 R3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms.

[0661] Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group.

[0662] R 3-3 , R 3-4 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, examples of which include 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, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred.

[0663] Among them, R 3-3 , R 3-4 are each independently 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.

[0664] As the repeating unit represented by formula (3-1), the following structures can be exemplified as preferred ones.

[0665] [ka]

[0666] [ka]

[0667] The content of the repeating unit represented by formula (3-1) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0668] If the content of the repeating unit of formula (3-1) is more than 70 mass%, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (3-1) is less than 5 mass%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0669] Depending on the application, a fluorine-containing resin film can also be formed by a method of applying pressure to the fluorine-containing resin as it is under heat without dissolving it in a solvent (hot pressing method), etc. In this case, even if more than 70 mass % of the repeating unit represented by formula (3-1) is used, the resistance of the fluorine-containing resin as a whole to UV ozone treatment or oxygen plasma treatment and the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment are not deteriorated, and such use is not prevented in the third embodiment of the present disclosure.

[0670] Here, the effects of the repeating unit represented by formula (3-1) according to the third embodiment of the present disclosure are not clear, but are presumed to be as follows: However, the third embodiment of the present disclosure is not limited to the effects described here.

[0671] The repeating unit represented by the formula (3-1) has the effect of imparting liquid repellency to the fluorine-containing resin after UV ozone treatment or oxygen plasma treatment. 3-3 or R 3-4 When is a fluorine atom, a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched fluoroalkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms, this effect is particularly large and is therefore preferably used.

[0672] Furthermore, the repeating unit represented by the formula (3-1) has the effect of improving the resistance of the fluorine-containing resin to UV ozone treatment or oxygen plasma treatment, and the reason for this is thought to be as follows.

[0673] In general, ester bonds are said to be susceptible to UV ozone treatment or oxygen plasma treatment and have low resistance (see also comparative fluororesin films 3-1 to 3-10 and Tables 3-12 to 3-15 described later). Therefore, in a fluoropolymer consisting only of an acrylic moiety having an ester bond adjacent to the main chain, the ester bond serves as a reactive site, which is thought to result in the fluoropolymer itself having low resistance to the UV treatment (for example, the fluoropolymers described in Patent Documents 3 and 4).

[0674] In contrast, the repeating unit represented by the formula (3-1) according to the third embodiment of the present disclosure has a structure consisting of hydrocarbons that do not have a substituent that mainly contains oxygen, such as an ester bond, which is susceptible to UV ozone treatment or oxygen plasma treatment. Therefore, it is considered that the inclusion of the repeating unit represented by the formula (3-1) in a resin has the effect of improving the resistance of the fluorine-containing resin according to the third embodiment of the present disclosure to the treatment.

[0675] 3-1-2. Repeating unit represented by formula (3-2) Next, the repeating unit represented by formula (3-2) will be described.

[0676] In formula (3-2), R 3-5 , R 3-6each independently represents a hydrogen atom or a methyl group.

[0677] In equation (3-2), W 3 represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

[0678] W 3 is —OC(═O)—NH—, this is one of the particularly preferred embodiments because the fluorine-containing resin according to the third embodiment of the present disclosure has better ink repellency after UV ozone treatment or oxygen plasma treatment.

[0679] In formula (3-2), A 3-1 , A 3-2 each independently represents a divalent linking group, and represents 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3.

[0680] Divalent linking group A 3-1 , A 3-2 are each independently a linear alkylene group having 1 to 10 carbon atoms, examples of which 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.

[0681] Divalent linking group A 3-1 , A 3-2 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.

[0682] Divalent linking group A3-1 , A 3-2 When each of the groups independently represents a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a 4-tert-butylcyclohexyl group.

[0683] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene group include a 1-hydroxyethylene group (-CH(OH)CH-), a 2-hydroxyethylene group (-CHCH(OH)-), a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CHOH)CH-), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CHOH)CHCH-), a hydroxy-isobutylene group (-CHCH(CHOH)CH-), and a hydroxy-tert-butylene group (-C(CHOH)(CH)CH-).

[0684] Furthermore, when any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, examples of the substituted alkylene group include the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above, in which the hydroxyl groups are replaced with -OC(=O)-CH3.

[0685] Among them, the divalent linking group A 3-1 , A 3-2are each independently a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH2OH)CH2-), a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CH 2OH)CH2CH2-), is preferred, with an ethylene group, a propylene group, a 1-hydroxyethylene group (-CH(OH)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, and a hydroxy-isopropylene group (-CH(CH2OH)CH2-) being more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH2-), and a 2-hydroxyethylene group (-CH2CH(OH)-) being particularly preferred.

[0686] In formula (3-2), Y 3-1 , Y 3-2 represents a divalent linking group, each independently representing -O- or -NH-, and more preferably -O-.

[0687] In formula (3-2), n represents an integer of 1 to 3, and n is particularly preferably 1.

[0688] In formula (3-2), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0689] As the repeating unit represented by formula (3-2), the following structures can be exemplified as preferred ones.

[0690] [ka]

[0691] [ka]

[0692] [ka]

[0693] [ka]

[0694] [ka]

[0695] The content of the repeating unit represented by formula (3-2) in the fluororesin is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0696] If the content of the repeating unit of formula (3-2) is more than 70% by mass, the fluororesin tends to be less soluble in a solvent, whereas if the content of the repeating unit of formula (3-1) is less than 5% by mass, the adhesion of the fluororesin film or bank obtained from the fluororesin to the substrate tends to decrease.

[0697] Although the effect of the repeating unit represented by formula (3-2) according to the third embodiment of the present disclosure is not clear, it is presumed that the inclusion of the repeating unit represented by formula (3-2) in the fluorine-containing resin improves the adhesion of the resulting fluorine-containing resin film or bank to the substrate. However, the third embodiment of the present disclosure is not limited to the effects described here.

[0698] As described above, the fluorine-containing resin according to the third embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (3-1) and a repeating unit represented by the formula (3-2) and another copolymer containing a repeating unit represented by the formula (3-1) and a repeating unit represented by the formula (3-2). In particular, the fluorine-containing resin according to the third embodiment of the present disclosure may be a mixture (blend) of a copolymer containing a repeating unit represented by the formula (3-2) and a repeating unit represented by the formula (3-1). 3a fluorine-containing resin containing a repeating unit in which W in formula (3-2) is -OC(=O)-NH-; 3 In one preferred aspect of the third embodiment of the present disclosure, the copolymer is a mixture with a fluorine-containing resin containing a repeating unit in which:

[0699] 3-1-3. Repeating unit represented by formula (3-3) The fluorine-containing resin according to the third embodiment of the present disclosure preferably further contains a repeating unit represented by formula (3-3).

[0700] The fluorine-containing resin may be a polymer in which a repeating unit represented by formula (3-3) is combined with a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2).

[0701] The fluorine-containing resin may also be a mixture (blend) of a polymer containing a repeating unit represented by formula (3-3) and a polymer containing a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). In the case of a mixture, it may also be a mixture of a polymer containing a repeating unit represented by formula (3-3) and a repeating unit represented by formula (3-1) and a polymer containing a repeating unit represented by formula (3-2), or a mixture of a polymer containing a repeating unit represented by formula (3-3) and a repeating unit represented by formula (3-2) and a polymer containing a repeating unit represented by formula (3-1).

[0702] [ka]

[0703] In formula (3-3), R 3-7 represents a hydrogen atom or a methyl group.

[0704] In formula (3-3), R 3-8represents 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 repeating unit is 30 mass% or more.

[0705] R 3-8 When 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.

[0706] R 3-8 When is a linear hydrocarbon group, the repeating unit represented by the formula (3-3) is preferably a repeating unit represented by the following formula (3-3-1):

[0707] [ka] (In the formula, R 3-7 is R in equation (3-3). 3-7 X is a hydrogen atom or a fluorine atom. p is an integer from 1 to 4. q is an integer from 1 to 14.

[0708] In the repeating unit represented by formula (3-3-1), it is particularly preferred that p is an integer of 1 to 2, q is an integer of 2 to 8, and X is a fluorine atom.

[0709] As the repeating unit represented by formula (3-3), the following structures can be exemplified as preferred ones.

[0710] [ka]

[0711] [ka]

[0712] [ka]

[0713] [ka]

[0714] The content of the repeating unit represented by formula (3-3) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, and particularly preferably from 10 to 30% by mass, relative to 100% by mass of the fluororesin.

[0715] If the content of the repeating unit of formula (3-3) is more than 70 mass %, the fluorine-containing resin tends to become less soluble in the solvent.

[0716] The repeating unit represented by formula (3-3) is a repeating unit that imparts liquid repellency to the fluorine-containing resin against ink after UV ozone treatment or oxygen plasma treatment. Therefore, when high liquid repellency against ink is desired, it is preferable that the fluorine-containing resin according to the third embodiment of the present disclosure contains a repeating unit represented by formula (3-3).

[0717] 3-1-4. Repeating unit represented by formula (3-4) The fluorine-containing resin according to the third embodiment of the present disclosure preferably further contains a repeating unit represented by formula (3-4).

[0718] The fluorine-containing resin may be a polymer in which a repeating unit represented by formula (3-4) is combined with a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). Alternatively, the fluorine-containing resin may be a polymer in which a repeating unit represented by formula (3-4) is combined with a repeating unit represented by formula (3-1), a repeating unit represented by formula (3-2), and a repeating unit represented by formula (3-3).

[0719] The fluorine-containing resin may also be a mixture (blend) of a polymer containing a repeating unit represented by formula (3-4) and a polymer containing a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). In the case of a mixture, it may also be a mixture of a polymer containing a repeating unit represented by formula (3-4) and a repeating unit represented by formula (3-1) and a polymer containing a repeating unit represented by formula (3-2), or a mixture of a polymer containing a repeating unit represented by formula (3-4) and a repeating unit represented by formula (3-2) and a polymer containing a repeating unit represented by formula (3-1). Furthermore, when the fluorine-containing resin is a mixture containing a repeating unit represented by formula (3-3), it may also be a mixture that can be considered as a combination of the repeating units represented by formulas (3-1) to (3-4).

[0720] [ka]

[0721] In formula (3-4), R 3-5 , Y 3-1 , A 3-1 and r is R in the formula (3-2). 3-5 , Y 3-1 , A 3-1 and r, respectively. Specific examples and preferred types of repeating units are the same as those listed in "3-1-2. Repeating units represented by formula (3-2)."

[0722] In formula (3-4), E 3-1 represents a hydroxyl group, a carboxyl group, or an oxirane group. E 3-1 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.

[0723] In formula (3-4), s represents 0 or 1. When s is 0, (-Y3-1 -A 3-1 -) represents a single bond. When r is 0 and s is 0, the main chain of the repeating unit does not contain E 3-1 The resulting structure is a bonded structure.

[0724] Furthermore, the repeating unit of formula (3-4) may be a repeating unit represented by the following formula (3-6).

[0725] [ka]

[0726] In formula (3-6), R 3-6 , Y 3-1 is R in the formula (3-2). 3-6 , Y 3-1 are synonymous with each other.

[0727] As the repeating unit represented by formula (3-4), the following structures can be exemplified as preferred ones.

[0728] [ka]

[0729] In formula (3-4), E 3-1 is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (3-4) imparts solubility to the fluorine-containing resin in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from the fluorine-containing resin, the fluorine-containing resin according to the third embodiment of the present disclosure is 3-1 is a hydroxyl group or a carboxyl group. In particular, when it is desired to form a bank containing both the repeating unit represented by formula (3-1) and the repeating unit represented by formula (3-2A) in the third embodiment of the present disclosure, it is preferable to use a repeating unit represented by formula (3-4) in which E 3-1 Further containing a repeating unit represented by formula (3-4) in which is a hydroxyl group or a carboxyl group tends to improve the shape of the pattern film, which is one of the preferred embodiments.

[0730] 3-1-5. Repeating unit represented by formula (3-5) The fluorine-containing resin according to the third embodiment of the present disclosure preferably further contains a repeating unit represented by formula (3-5).

[0731] The fluorine-containing resin may be a polymer in which a repeating unit represented by formula (3-5) is combined with a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). Alternatively, the fluorine-containing resin may be a polymer in which a repeating unit represented by formula (3-5) is combined with a repeating unit represented by formula (3-1), a repeating unit represented by formula (3-2), and a repeating unit represented by formula (3-3).

[0732] The fluorine-containing resin may also be a mixture (blend) of a polymer containing a repeating unit represented by formula (3-5) and a polymer containing a repeating unit represented by formula (3-1) and a repeating unit represented by formula (3-2). In the case of a mixture, it may also be a mixture of a polymer containing a repeating unit represented by formula (3-5) and a repeating unit represented by formula (3-1) and a polymer containing a repeating unit represented by formula (3-2), or a mixture of a polymer containing a repeating unit represented by formula (3-5) and a repeating unit represented by formula (3-2) and a polymer containing a repeating unit represented by formula (3-1). Furthermore, when the fluorine-containing resin is a mixture containing a repeating unit represented by formula (3-3), it may also be a mixture that can be considered as a combination of the repeating units represented by formulas (3-1) to (3-5).

[0733] [ka]

[0734] In formula (3-5), R 3-9 represents a hydrogen atom or a methyl group.

[0735] In formula (3-5), B 3are each independently a hydroxyl group, a carboxyl group, -C(=O)-OR 3-10 (R 3-10 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, and R 3-10 The fluorine content in the alkyl group is 30 mass % or more. 3-11 (R 3-11 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.

[0736] B 3 -C(=O)-OR 3-10 When R 3-10 For specific examples, see R in formula (3-3). 3-8 The same can be mentioned here again.

[0737] B 3 -OC(=O)-R 3-11 When R 3-11 Examples of the alkyl group include 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 methyl group is more preferred.

[0738] In the formula (3-5), m represents an integer of 0 to 3.

[0739] As the repeating unit represented by formula (3-5), the following structures can be exemplified as preferred ones.

[0740] [ka]

[0741] [ka]

[0742] The content of the repeating unit represented by formula (3-5) is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and particularly preferably 20% by mass or more and 40% by mass or less, relative to 100% by mass of the fluororesin.

[0743] If the content of the repeating unit of formula (3-5) is more than 70 mass %, the fluorine-containing resin tends to become less soluble in the solvent.

[0744] In formula (3-5), B 3 is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (3-5) imparts solubility to the fluorine-containing resin in an alkaline developer. Therefore, when it is desired to impart alkaline developability to a film obtained from the fluorine-containing resin, the fluorine-containing resin according to the third embodiment of the present disclosure may contain B 3 is a hydroxyl group or a carboxyl group. In particular, when it is desired to form a bank containing both the repeating unit represented by formula (3-1) and the repeating unit represented by formula (3-2A) in the third embodiment of the present disclosure, it is preferable to use a repeating unit represented by formula (3-5) in which B 3 Further containing a repeating unit represented by formula (3-5) in which is a hydroxyl group or a carboxyl group tends to improve the shape of the pattern film, which is one of the preferred embodiments.

[0745] 3-1-6.Preferred embodiments of fluorine-containing resin Among the fluorine-containing resins according to the third embodiment of the present disclosure, the following six embodiments can be mentioned as being particularly preferable.

[0746] <Aspect 3-1> A fluorine-containing resin containing both a repeating unit represented by the following formula (3-1) and a repeating unit represented by the following formula (3-2): Formula (3-1): R 3-1 and R 3-2is a hydrogen atom, R 3-3 、 R 3-4 each independently represents a fluorine atom, a difluoromethyl group, or a trifluoromethyl group, Formula (3-2):R 3-5 and R 3-6 are each independently a hydrogen atom or a methyl group, W 3 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 3-1 , A 3-2 are each independently an ethylene group, Y 3-1 and Y 3-2 is -O-, n is 1, r is 1

[0747] <Aspect 3-2> A fluorine-containing resin containing both a repeating unit represented by the following formula (3-1) and a repeating unit represented by the following formula (3-2): Formula (3-1): Same as embodiment 3-1 Formula (3-2): R 3-5 and R 3-6 are each independently a hydrogen atom or a methyl group, W 3 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 3-1 , A 3-2 are each independently an ethylene group, a 1-hydroxy-n-ethylene group (-CH(OH)CH2-) or a 2-hydroxy-n-ethylene group (-CH2CH(OH)-), Y 3-1 and Y 3-2 is -O-, n is 1, r is 1

[0748] <Aspect 3-3> A fluorine-containing resin containing both a repeating unit represented by the following formula (3-1) and a repeating unit represented by the following formula (3-2): Formula (3-1): Same as embodiment 3-1 Formula (3-2): R 3-5 and R 3-6 are each independently a hydrogen atom or a methyl group, W 3 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 3-1 , A3-2 each independently represents an ethylene group or a butyl group; Y 3-1 and Y 3-2 is -O-, n is 1, r is 0

[0749] <Aspect 3-4> Fluorine-containing resin containing repeating units represented by the following formulas (3-1), (3-2) and (3-3-1): Formula (3-1): Same as embodiment 3-1 Formula (3-2): Same as embodiment 3-1 Formula (3-3-1):R 3-7 is a methyl group, p is 2, q is an integer from 4 to 8, and X is a fluorine atom

[0750] <Aspect 3-5> Fluorine-containing resins containing repeating units represented by the following formulas (3-1), (3-2), (3-3-1) and (3-4): Formula (3-1): Same as embodiment 3-1 Formula (3-2): Same as embodiment 3-1 Formula (3-3-1): Same as aspect 3-4 Formula (3-4):R 3-5 , Y 3-1 , A 3-1 and r is the same as in embodiment 1, s is 1, E 3-1 is a hydroxyl or carboxyl group

[0751] <Aspect 3-6> Fluorine-containing resins containing repeating units represented by the following formulae (3-1), (3-2), (3-3-1), (3-4) and (3-5): Formula (3-1): Same as embodiment 3-1 Formula (3-2): Same as embodiment 3-1 Formula (3-3-1): Same as aspect 3-4 Formula (3-4): Same as embodiment 3-5 Formula (3-5):R 3-9 is a hydrogen atom, B 3 is a hydroxyl group, a carboxyl group or -OC(=O)-CH3, m is 1

[0752] 3-1-7. Manufacturing method of fluorine-containing resin The fluorine-containing resin according to the third embodiment of the present disclosure can be easily produced through two steps, by polymerizing monomers represented by formula (3-1a) and formula (3-2a) to obtain a fluorine-containing resin precursor containing repeating units represented by formula (3-1) and formula (3-2b), and then subjecting formula (3-2b) in the repeating units represented by formula (3-1) and formula (3-2b) to an addition reaction with an acrylic acid derivative represented by formula (3-2c).

[0753] [ka] [In formula (3-1), R 3-1 represents a hydrogen atom, a fluorine atom or a methyl group. R 3-2 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. R 3-3 , R 3-4 each independently represents a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear fluoroalkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic fluoroalkyl group having 3 to 10 carbon atoms. Furthermore, R 3-1 , R 3-3 , R 3-4 is a fluorine atom or the above-mentioned fluoroalkyl group. R in formula (3-1a) 3-1 , R 3-2 , R 3-3 and R 3-4 is R in formula (3-1). 3-1 , R 3-2 , R 3-3 and R 3-4 are synonymous with each other. In formula (3-2), R 3-5 , R 3-6 each independently represents a hydrogen atom or a methyl group. W represents a divalent linking group, and represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. A 3-1 , A 3-2 represents a divalent linking group, each independently representing 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, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. Y 3-1 , Y 3-2 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1. In formula (3-2a), R 3-5 , Y 3-1 , A 3-1 and r is R in formula (3-2). 3-5 , Y 3-1 , A 3-1 and r, respectively. E 3-2 represents a hydroxyl group or an ethylene oxide group. R in formula (3-2b) 3-5 , Y 3-1 , A 3-1 , r and E 3-2 is R in formula (3-2). 3-5 , Y 3-1 , A 3-1 , r and E in formula (3-2a) 3-2 are synonymous with each other. R in formula (3-2c) 3-6 , Y 3-2 , A 3-2 and n is R in formula (3-2). 3-6 , Y 3-2 , A 3-2 and n, respectively. Z 3 represents an isocyanate group (-N=C=O), an acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group), an acid anhydride, a halogen atom, a hydroxyl group, an amino group (-NH), or an oxirane group.

[0754] Each step will be explained below. [First step] The first step is a step of polymerizing monomers represented by formula (3-1a) and formula (3-2a) to produce a fluorine-containing resin precursor containing repeating units represented by formula (3-1) and formula (3-2b).

[0755] [ka]

[0756] The monomer represented by formula (3-1a) may be a commercially available product and used as is, or may be prepared by a known method or a method similar thereto. For example, it is preferable to prepare it by the method described in Journal of Organic Chemistry, 1970, Vol. 35, No. 6, pp. 2096-2099, or a method similar thereto.

[0757] The repeating unit represented by formula (3-1) is formed by cleavage of the polymerizable double bond of the monomer represented by formula (3-1a). In the polymerization reaction, no change occurs in the structure other than the polymerizable double bond, and the original structure is maintained. Therefore, in the monomer represented by formula (3-1a), R 3-1 , R 3-2 , R 3-3 and R 3-4 In the repeating unit represented by formula (3-1), R 3-1 , R 3-2 , R 3-3 and R 3-4 and the specific substituents are the same as those listed in "3-1-1. Repeating unit represented by formula (3-1)." Furthermore, as for the preferred structure of the monomer represented by formula (3-1a), the structures of the corresponding monomers before cleavage of the polymerizable double bond in the repeating units exemplified in "3-1-1. Repeating unit represented by formula (3-1)" can be listed again here.

[0758] The monomer represented by formula (3-2a) may be a commercially available product and used as is, or may be prepared by a known method or a method similar thereto. It is preferable to use a commercially available product because it is easily available.

[0759] The repeating unit represented by formula (3-2b) is formed by cleavage of the polymerizable double bond of the monomer represented by formula (3-2a). In the polymerization reaction, no changes occur in the structure other than the polymerizable double bond, and the original structure is maintained.

[0760] In the monomer represented by formula (3-2a), E 3-2 represents a hydroxyl group or an ethylene oxide group. 3-5 is a hydrogen atom or a methyl group, A 3-1 is an ethylene group, Y 3-1 -O-, E 3-2 is preferably a hydroxyl group, and r is preferably 0 or 1.

[0761] The polymerization method of the monomers represented by formula (3-1a) and formula (3-2a) will be described. The polymerization method is not particularly limited as long as it is a commonly used method, but radical polymerization and ionic polymerization are preferred, and in some cases, coordination anionic polymerization, living anionic polymerization, cationic polymerization, ring-opening metathesis polymerization, vinylene polymerization, vinyl addition, etc. can also be used. Among these, radical polymerization is particularly preferred. Well-known methods can be applied as each polymerization method. Below, a radical polymerization method will be described, but other methods can also be easily polymerized according to well-known literature, etc.

[0762] The radical polymerization may be carried out in the presence of a radical polymerization initiator or a radical initiation source by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, in a batch, semi-continuous, or continuous operation.

[0763] The radical polymerization initiator is not particularly limited, but examples include azo compounds, peroxide compounds, persulfate compounds, and redox compounds. In particular, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), tert-butyl peroxypivalate, di-tert-butyl peroxide, isobutyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, tert-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, ammonium persulfate, and the like are preferred.

[0764] The reaction vessel used for the polymerization reaction is not particularly limited. In addition to the monomer and initiator, a polymerization solvent is preferably used in the polymerization reaction. The polymerization solvent is preferably one that does not inhibit radical polymerization. Typical examples include esters such as ethyl acetate and n-butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; hydrocarbons such as toluene and cyclohexane; and alcohols such as methanol, isopropyl alcohol, and ethylene glycol monomethyl ether. Solvents such as water, linear ethers, cyclic ethers, fluorocarbons, and aromatic solvents can also be used. The polymerization solvent can be used alone or in combination. A molecular weight modifier such as mercaptan can also be used. The reaction temperature for the polymerization reaction varies depending on the radical polymerization initiator or radical polymerization initiation source. It is generally preferred that the temperature be 20°C to 200°C, more preferably 30°C to 140°C, and particularly preferably 50°C to 120°C.

[0765] The polymerization time is usually 0.1 to 48 hours, preferably 1 to 24 hours, but it is preferable to use analytical equipment such as high performance liquid chromatography (HPLC) or nuclear magnetic resonance (NMR) to determine the end point of the polymerization when the monomer is consumed. After the polymerization is completed, the reaction can be stopped by cooling the polymerization solution to below room temperature.

[0766] The monomer concentration at the start of polymerization relative to 100% by mass of the polymerization reaction system is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. If the monomer concentration is lower than this range, the reaction rate of the polymerization reaction tends to decrease, and if the concentration is higher than this range, the viscosity of the polymerization liquid tends to increase.

[0767] Methods for removing the organic solvent or water from the obtained solution or dispersion of the fluororesin precursor include reprecipitation, filtration, distillation by heating under reduced pressure, etc. The obtained fluororesin precursor may be further purified by, for example, washing with a solvent in which the fluororesin is insoluble during filtration.

[0768] [Second process] The second step is a step of producing a fluorine-containing resin containing repeating units represented by formula (3-1) and formula (3-2) by addition reaction of the repeating units represented by formula (3-2b) with an acrylic acid derivative represented by formula (3-2c).

[0769] [ka]

[0770] The acrylic acid derivative represented by formula (3-2c) can be a commercially available product and used as is, or can be prepared by a known method or a method similar thereto. It is preferable to use a commercially available product because it is easily available.

[0771] R in formula (3-2c) 3-6 , Y 3-2 , A 3-2 and n is R in formula (3-2). 3-6 , Y 3-2 , A 3-2 and n have the same meaning as R and n, respectively. Specific substituents are as described in "3-1-2. Repeating units represented by formula (3-2)". 3-6 , Y 3-2 and A 3-2 can again be mentioned here.

[0772] Z 3 represents an isocyanate group (-N=C=O), acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group), acid anhydride, halogen atom, hydroxyl group or a hydroxyl group protected by a protecting group, amino group (-NH2), or oxirane group.

[0773] Z 3 Examples of the acid halide (-C(=O)-X, where X is a halogen atom or an imidazolyl group) in the formula (I) include acid fluorides such as -C(=O)-F, -C(=O)-Cl, -C(=O)-Br, and -C(=O)-I, and groups in which -C(=O)- and a 2-imidazolyl group are linked together.

[0774] Z 3 Examples of the acid anhydride in the formula include -C(=O)-OC(=O)-CH3, -C(=O)-OC(=O)-C(CH3)3, and -C(=O)-OC(=O)-CF3.

[0775] Z 3 Examples of the hydroxyl group protected by a protecting group in the formula (I) include a hydroxyl group protected by a protecting group such as a methanesulfonyl group, a trifluoromethanesulfonyl group, or a p-toluenesulfonyl group.

[0776] Z 3 Examples of the oxirane group in the formula include an ethylene oxide group, a 1,2-propylene oxide group, and a 1,3-propylene oxide group.

[0777] Among them, Z 3 Particularly preferred are an isocyanate group, —C(═O)—Cl, and an ethylene oxide group.

[0778] As the acrylic acid derivative represented by formula (3-2c), the following structures can be exemplified as preferred examples.

[0779] [ka]

[0780] [ka]

[0781] This addition reaction occurs when Z in formula (3-2c) 3 Although the mode of reaction varies depending on the type of the compound, any mode of reaction can be carried out using a general addition reaction method. Two modes of reaction are shown below.

[0782] Aspect (3-1): E in formula (3-2b) 3-2 is a hydroxyl group, and Z in formula (3-2c) 3 When is an isocyanate group, W in the resulting formula (3-2) can form a bond of "-O-C(=O)-NH-".

[0783] Aspect (3-2): E in formula (3-2b) 3-2 is a hydroxyl group, and Z in formula (3-2c) 3 is an ethylene oxide group, W in the resulting formula (3-2) 3 can form a bond that results in "-O-".

[0784] The repeating units represented by formula (3-1) and formula (3-2b) may further include a repeating unit having a nucleophilic substituent such as a carboxyl group (for example, E 3-1 is a carboxyl group, or B in formula (3-4) 3 Even if the repeating unit (E in formula (3-2b) is a hydroxyl group or a carboxyl group) is contained, 3-2 selectively reacts with the acrylic acid derivative represented by formula (3-2c). 3 In equation (3-2b), E 3-2 This is because A in formula (3-2b) 3-1 and E 3-2 The reactivity varies depending on the type of E in formula (3-2b).3-2 When is a primary alcohol, its reactivity with formula (3-2c) is significantly high.

[0785] The production method of the second step will be described below. Regardless of which of the above embodiments is employed, the following method can usually be employed.

[0786] The amount of the acrylic acid derivative represented by formula (3-2c) used to react with the repeating units represented by formula (3-1) and formula (3-2b) is not particularly limited, but is usually 0.01 to 5 mol, preferably 0.05 to 3 mol, and more preferably 0.05 to 1 mol per 1 mol of the repeating units represented by formula (3-1) and formula (3-2b). It is particularly preferred that the amount of the acrylic acid derivative used is 0.2 to 1 mol.

[0787] The reaction is usually carried out in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, tetrahydrofuran, acetonitrile, propylene glycol monomethyl monoacetate (PGMEA), N,N-dimethylformamide, etc. These solvents may be used alone or in combination of two or more. The reaction temperature is not particularly limited and is usually in the range of −20 to +100° C., preferably 0 to +80° C., and more preferably +10 to +40° C. The reaction is preferably carried out with stirring.

[0788] The reaction time depends on the reaction temperature, but is usually from several minutes to 100 hours, preferably from 30 minutes to 50 hours, and more preferably from 1 to 20 hours. It is preferable to use an analytical instrument such as a nuclear magnetic resonance (NMR) spectrometer and determine the end point of the reaction when the acrylic acid derivative represented by general formula (3-2c) is consumed.

[0789] In this reaction, a base may be used as a catalyst. Preferred examples of the base catalyst include organic bases such as trimethylamine, triethylamine, tripropylamine, tributylamine, and diisopropylethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of such a base catalyst used is not particularly limited, but is 0.01 to 5 mol, preferably 0.02 to 3 mol, and more preferably 0.05 to 1 mol, per 1 mol of the repeating units represented by formula (3-1) and formula (3-2b).

[0790] After the reaction is completed, a fluororesin containing both the repeating unit represented by formula (3-1) and the repeating unit represented by formula (3-2) can be obtained by ordinary means such as reprecipitation, filtration, extraction, crystallization, recrystallization, etc. The obtained fluororesin may be further purified, for example by washing with a solvent in which the fluororesin is insoluble during filtration.

[0791] 3-2. Photosensitive resin composition The photosensitive resin composition according to the third embodiment of the present disclosure contains at least the above-described fluorine-containing resin, a solvent, and a photopolymerization initiator.

[0792] The photosensitive resin composition according to the third embodiment of the present disclosure is particularly suitable as a negative resin composition for obtaining a fluorine-containing resin film or a bank for organic EL devices, which will be described later.

[0793] The solvent in the photosensitive resin composition according to the third embodiment of the present disclosure is not particularly limited as long as it dissolves the fluorine-containing resin, and examples thereof include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, fluorine-containing solvents, etc. These may be used alone or in combination of two or more.

[0794] Specific examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. Specific 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.

[0795] Specific 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), and the monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0796] Specific examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0797] Specific 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. Examples of aromatic solvents include xylene and toluene.

[0798] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0799] 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.

[0800] Among them, the solvents are 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 The solvent is preferably at least one selected from the group consisting of propylene glycol 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. Methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone are more preferred.

[0801] The amount of solvent in the photosensitive resin composition according to the third embodiment of the present disclosure is usually in the range of 50% by mass or more and 2,000% by mass or less relative to 100% by mass of the fluorine-containing resin concentration (however, when the photosensitive resin composition contains an alkali-soluble resin described below, the combined concentration of the resin is used). It is preferably 100% by mass or more and 1,000% by mass or less. By adjusting the amount of solvent, the thickness of the resin film to be formed can be adjusted, and within the above range, a resin film thickness suitable for obtaining a bank for organic electroluminescence (EL) can be obtained.

[0802] The photopolymerization initiator in the photosensitive resin composition according to the third embodiment of the present disclosure is not particularly limited as long as it polymerizes a monomer having a polymerizable double bond listed in "3-1-7. Production method for fluorine-containing resin" by electromagnetic waves or electron beams, and any known photopolymerization initiator can be used. As the photopolymerization initiator, a photoradical initiator or a photoacid initiator can be used, and these may be used alone, or a photoradical initiator and a photoacid initiator may be used in combination, or two or more types of photoradical initiators or photoacid initiators may be mixed and used. Furthermore, by using an additive together with the photopolymerization initiator, it is also possible to carry out living polymerization in some cases, and known additives can be used as the additive.

[0803] Photoradical initiators can be specifically classified into intramolecular cleavage types in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radical...

Claims

1. A method for producing a polymerizable composition comprising at least a fluorine-containing resin having a structure represented by the following formula (1-3) and / or a structure represented by the following formula (1-4), a solvent, and a photopolymerization initiator, the fluorine-containing resin contains a repeating unit composed of a hydrocarbon having a fluorine atom, A photosensitive resin composition characterized in that the repeating unit comprising a hydrocarbon having a fluorine atom has a structure represented by the following formula (1-2): 【Chemical 1】 (In formula (1-3), R 1-3 and R 1-4 each independently represent a hydrogen atom or a methyl group. W 1-1 represents a divalent linking group and represents -O-, -O-C(═O)-, -C(═O)-O-, -O-C(═O)-NH-, -C(═O)-O-C(═O)-NH- or -C(═O)-NH-. A 1-1 represents a divalent linking group and represents 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, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(═O)-CH 3 . Y 1-1 represents a divalent linking group and represents -O- or -NH-. n represents an integer of 1 to 3.) 【Chemistry 2】 (In formula (1-4), R 1-5 and R 1-6 each independently represent a hydrogen atom or a methyl group. W 1-2 represents a divalent linking group and is -O-, -O-C(═O)-, -C(═O)-O-, -O-C(═O)-NH-, -C(═O)-O-C(═O)-NH- or -C(═O)-NH-. A 1-2 and A 1-3 each independently represent a divalent linking group and are 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, in which any number of hydrogen atoms may be substituted with a hydroxyl group or -O-C(═O)-CH 3 . Y 1-2 and Y 1-3 represents a divalent linking group, and each independently represents -O- or -NH-. n represents an integer of 1 to 3. r represents 0 or 1. 【Chemistry 3】 (In formula (1-2), each Rf independently represents 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. R １－１ represents a hydrogen atom, a fluorine atom or a methyl group. １－２ 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.

2. 2. The photosensitive resin composition according to claim 1, wherein the fluorine content of the fluorine-containing resin is 20 to 50% by mass.

3. The photosensitive resin composition according to claim 1 or 2, further comprising a crosslinking agent.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising an alkali-soluble resin.

5. The photosensitive resin composition according to any one of claims 1 to 4, which is cured at a temperature of 140°C or less.

6. A method for producing a cured fluorine-containing resin product, comprising: A method for producing a cured fluorine-containing resin product, comprising a baking step of curing the photosensitive resin composition according to any one of claims 1 to 5 by baking at a temperature of 140°C or lower.

7. 7. The method for producing a cured fluorine-containing resin product according to claim 6, wherein the photosensitive resin composition is baked at 60 to 130° C. in the baking step.

8. 8. The method for producing a cured fluorine-containing resin product according to claim 6, further comprising, before the baking step, an exposure step of exposing the photosensitive resin composition to high-energy rays.

9. 9. The method for producing a cured fluorine-containing resin product according to claim 8, wherein the high-energy radiation is at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

10. A method for producing a cured fluorine-containing resin product, comprising: a film-forming step of applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate and then heating the composition to form a fluorine-containing resin film; an exposure step of exposing the fluorine-containing resin film to high-energy rays; a developing step of developing the fluorine-containing resin film after the exposure step with an alkaline aqueous solution to form a fluorine-containing resin patterned film; a baking step of baking the fluorine-containing resin patterned film at a temperature of 140°C or less to cure the film, after the developing step, to form a fluorine-containing resin cured product.

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