Fluorine-containing resin, liquid repellent agent, photosensitive resin composition, cured product, and display

Abstract

The present invention provides a fluorine-containing resin which can produce a bank (partition wall) whose liquid repellency is not easily reduced even if UV ozone treatment or oxygen plasma treatment is performed. The fluorine-containing resin of the present invention is characterized by containing a repeating unit (U) which includes a monomer (A) having a triple bond in a side chain as a monomer unit.

Description

Technical Field

[0001] This invention relates to fluorinated resins, liquid repellents, photosensitive resin compositions, cured products, and displays. Background Technology

[0002] In the manufacture of display elements such as organic EL displays, micro LED displays, and quantum dot displays, inkjet printing is a known method for forming organic layers with functions such as light emission. There are several methods of inkjet printing. Specifically, one method involves applying ink through a nozzle to the recesses of a patterned film with uneven surfaces formed on a substrate and then curing it. Another method involves pre-forming a patterned film on the substrate in the form of hydrophilic and hydrophobic portions, and then applying droplets of ink to the patterned film, allowing only the hydrophilic portions to adhere to the ink. The hydrophilic portions are areas wetted by the ink, and the hydrophobic portions are areas that repel the ink.

[0003] In particular, regarding the method described above of applying ink to the recesses of a patterned film through a nozzle and then curing it, two main methods can be used to create such a patterned film with raised and recessed areas. One method is photolithography, which involves exposing the surface of a photosensitive resist film coated on a substrate in a patterned manner to form exposed and unexposed areas, and then removing any areas by dissolving them with a developer. The other method is imprinting, which uses printing technology. Typically, after forming the patterned film with raised and recessed areas, the entire surface of the substrate is subjected to UV ozone treatment or oxygen plasma treatment. This UV ozone treatment or oxygen plasma treatment is particularly effective in removing residual organic matter from the recesses of the patterned film and reducing uneven wetting of the applied ink, thereby preventing defects in the display element in advance.

[0004] The raised portions of the patterned film with its uneven surface are called banks. When ink is dropped into the recesses of the patterned film, the banks act as barriers to prevent the ink from mixing. To enhance this barrier effect, the substrate surface of the recesses of the patterned film must be exposed, its surface must be hydrophilic to the ink, and the upper surface of the banks must be liquid repellent to the ink.

[0005] Fluorinated resins can be used as the resins used to form this barrier. By using fluorinated resins, the liquid repellency is increased.

[0006] Patent Document 1 discloses a photoresist composition containing a fluorinated resin, comprising: a fluorinated resin (A) having monomer units formed from monomers represented by Formula 1 and having a fluorine atom content of 7 to 35% by mass; and a photosensitive component that reacts with light of wavelengths of 100 to 600 nm. The photoresist composition is characterized in that the proportion of the fluorinated resin (A) is 0.1 to 30% by mass relative to the total solids content of the photoresist composition. The photosensitive component comprises: a photoacid generator (B); an alkali-soluble resin (C) having carboxyl and / or phenolic hydroxyl groups; and an acid crosslinking agent (D), which is a compound having two or more groups that can react with carboxyl or phenolic hydroxyl groups through the action of an acid. CH2=C(R 1 COOXR f …Formula 1 In Equation 1, R 1 Represents a hydrogen atom, methyl or trifluoromethyl group, where X represents a divalent organic group with 1 to 6 carbon atoms and no fluorine atom, and R represents a hydrogen atom, methyl group, or trifluoromethyl group. f It refers to perfluoroalkyl groups with 4 to 6 carbon atoms.

[0007] Patent Document 2 discloses an ink repellent containing a fluorine-containing polymeric unit, characterized in that it comprises a polymer having a polymeric unit (b1) and a polymeric unit (b2), wherein the polymeric unit (b1) has at least one alkyl group having 20 or fewer carbon atoms that has been replaced by a fluorine atom (wherein the alkyl group includes an alkyl group having an ether-like oxygen), the polymeric unit (b2) has an olefinic double bond, and the ink repellent has a fluorine content of 5 to 25% by mass and a number average molecular weight of 500 or more and less than 10,000.

[0008] As a resist composition containing fluorinated resin, Patent Document 3 discloses a resist composition comprising a monomer unit formed by a monomer represented by Formula 1, a fluorinated resin (A) having an olefinic double bond and a fluorine atom content of 7 to 35% by mass, and a photosensitive component that reacts to light with a wavelength of 100 to 600 nm. The resist composition is characterized in that the proportion of the fluorinated resin (A) relative to the total solid content of the resist composition is 0.1 to 30% by mass, and the photosensitive component comprises a photoradical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more olefinic double bonds within one molecule. CH2=C(R 1 COOXR f …Formula 1 In Equation 1, R 1 Represents a hydrogen atom, methyl or trifluoromethyl group, where X represents a divalent organic group with 1 to 6 carbon atoms and no fluorine atom, and R represents a hydrogen atom, methyl group, or trifluoromethyl group. fIt refers to perfluoroalkyl groups with 4 to 6 carbon atoms.

[0009] Patent Document 4 discloses a negative photosensitive resin composition containing an ink repellent having fluorine atoms. The negative photosensitive resin composition contains a photocurable alkali-soluble resin or alkali-soluble monomer (A), a photoradical polymerization initiator (B), a photoacid generator (C), an acid curing agent (D), and an ink repellent having fluorine atoms (E). The negative photosensitive resin composition is characterized in that the fluorine atoms in the ink repellent (E) have a content of 1 to 40% by mass, and the ink repellent (E) has an olefinic double bond.

[0010] As a photosensitive resin composition with good liquid repellency, Patent Document 5 discloses a photosensitive resin composition characterized by comprising at least a fluorinated resin having a crosslinking site, a solvent, and a photopolymerization initiator, wherein the fluorinated resin contains repeating units formed from hydrocarbons having fluorine atoms. Existing technical documents Patent documents

[0011] Patent Document 1: Japanese Patent No. 4474991 Patent Document 2: Japanese Patent No. 4488098 Patent Document 3: Japanese Patent No. 4905563 Patent Document 4: Japanese Patent No. 6536578 Patent Document 5: International Publication No. 2020 / 110793 Summary of the Invention The technical problem to be solved by the present invention

[0012] When using the corrosion-resistant compositions described in Patent Documents 1 to 4 to manufacture a dike (partition wall), the cured resin has excellent liquid repellency, but the following problem exists: the liquid repellency decreases when subjected to the above-mentioned UV ozone treatment or oxygen plasma treatment.

[0013] The technical problem of the present invention is to provide a fluorinated resin that can be used to make a barrier (separator) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment. Technical means to solve technical problems

[0014] The inventors of this application conducted careful research in view of the aforementioned problems. As a result, they discovered that the above-mentioned technical problems could be solved by using monomers with triple bonds in their side chains, thus completing this invention.

[0015] By using the fluorinated resin of the present invention, it is possible to produce a barrier (partition wall) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment.

[0016] That is, the present invention is as follows.

[0017] The fluorinated resin of the present invention is characterized by containing repeating units (U), which are contained in monomers (A) having triple bonds in their side chains as monomer units.

[0018] The fluorine atom content of the fluorine-containing resin of the present invention is preferably 5% by mass or more.

[0019] The fluorinated resin of the present invention preferably contains fluorine atoms in the side chains of at least a portion of the monomer (A) described above.

[0020] In the fluorinated resin of the present invention, preferably at least a portion of the triple bond is a carbon-nitrogen triple bond of a cyano group.

[0021] In the fluorinated resin of the present invention, preferably at least a portion of the above monomer (A) has the structure represented by the following formula (1) or formula (1'). CH2=C(R 1 )C≡CR 2 …(1) CH2=C(R 1 )XC≡CR 2 …(1') In equations (1) and (1'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R 2 The alkyl group refers to a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.

[0022] In the fluorinated resin of the present invention, the structure represented by the above formula (1) or (1') is preferably the structure represented by the following formula (2) or formula (2'). CH2=C(R 1 )C≡CR f …(2) CH2=C(R 1 )XC≡CR f …(2') In equations (2) and (2'), R 1Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to a straight-chain perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.

[0023] In the fluorinated resin of the present invention, the repeating unit (U) preferably comprises the monomer (A) and a monomer (B) having the structure represented by the following formula (3) or formula (3') as a monomer unit. CH2=C(R 1 COOR 2 …(3) CH2=C(R 1 COOXR 2 …(3') In equations (3) and (3'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R 2 The alkyl group refers to a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.

[0024] In the fluorinated resin of the present invention, the structure represented by the above formula (3) or formula (3') is preferably the structure represented by the following formula (4) or formula (4'). CH2=C(R 1 COOR f …(4) CH2=C(R 1 COOXR f …(4') In equations (4) and (4'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R fIt refers to a straight-chain perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.

[0025] The liquid repellent of the present invention is characterized by comprising the fluorinated resin of the present invention described above.

[0026] The photosensitive resin composition of the present invention is characterized in that it comprises at least the fluorinated resin, solvent and photopolymerization initiator of the present invention described above.

[0027] The photosensitive resin composition of the present invention preferably further comprises a crosslinking agent and an alkali-soluble resin.

[0028] The photosensitive resin composition of the present invention is preferably used for the formation of partition walls.

[0029] The cured product of the present invention is characterized in that it is cured from the above-described photosensitive resin composition of the present invention.

[0030] The display of the present invention is characterized by including a light-emitting element, the light-emitting element comprising: The partition wall formed by the cured product of the present invention described above; and A light-emitting layer disposed in the region divided by the aforementioned partition wall.

[0031] The display of the present invention is preferably an organic EL display or a quantum dot display. Invention Effects

[0032] According to the present invention, a barrier (partition wall) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment can be manufactured. Detailed Implementation

[0033] The present invention will now be described in detail, but the description of the constituent elements described below is only one example of an embodiment of the invention, and the invention is not limited to these specific contents. Various changes can be made within its scope.

[0034] In the "Detailed Implementation" section of this specification, items represented by "[" and "]", "<" and ">" are merely symbols and have no meaning in themselves. In this specification, "polymer" and "resin" are synonyms and, unless otherwise stated, refer to high molecular weight compounds.

[0035] In this specification, "dike" and "separator" are synonyms and, unless otherwise stated, both refer to the raised portion of a patterned film with raised and recessed surfaces in inkjet printing.

[0036] (Fluoropolymer) The fluorinated resin of the present invention is characterized by containing repeating units (U), which are contained in monomers (A) having triple bonds in their side chains as monomer units.

[0037] By using the fluorinated resin of this invention, a barrier (separator) with sufficiently high liquid repellency can be produced. Furthermore, the liquid repellency of the produced barrier (separator) does not easily decrease even after UV ozone treatment or oxygen plasma treatment. Furthermore, the reasons why it is possible to create a dike (partition wall) with sufficiently high liquid repellency are predicted as follows. First, it is believed that the liquid repellency will increase when fluorinated alkyl groups undergo surface segregation. As described below, when using the fluorinated resin of the present invention to make a barrier (separator), after forming the patterned film, a UV ozone treatment or an oxygen plasma treatment is performed, followed by a heat treatment. After forming a patterned film using the fluorinated resin of the present invention, UV ozone treatment or oxygen plasma treatment is performed, thereby immobilizing these functional groups by allowing the π electrons of the triple bonds to interact with the -CH, -OH, and -NH bonds. On the other hand, fluorinated alkyl groups, which have weaker interactions with the π electrons of the triple bonds, are prone to surface segregation. Subsequent heating promotes rearrangement and improves liquid repellency.

[0038] In this specification, "monomer (A) having a triple bond in its side chain" means a monomer that has a triple bond in the position of the side chain of the polymer when monomer (A) forms a polymer. In this specification, "repeating unit (U)" refers to a monomer unit constituting the main chain of a fluoropolymer, and specifically refers to multiple monomer units present in that main chain. Furthermore, the repeating units (U) can form the main chain of the fluoropolymer continuously, or the main chain of the fluoropolymer can be formed with other monomer units present between the repeating units (U). Additionally, monomer units other than repeating units (U) may be present at the ends of the main chain of the fluoropolymer.

[0039] The fluorine atom content of the fluorine-containing resin of the present invention is preferably 5% by mass or more. In addition, the content of fluorine atoms is preferably less than 50% by mass. When the fluorine atom content is 5% or more by mass, a barrier with higher liquid repellency can be made.

[0040] In addition, in this specification, "fluorine atom content of fluorinated resin" refers to the value calculated based on the molar ratio of the monomers constituting the fluorinated resin, the molecular weight of the monomers constituting the fluorinated resin, and the fluorine content contained in the monomers, as measured by NMR (nuclear magnetic resonance spectroscopy). Here, a method for determining the fluorine content of a fluorinated resin is described when the resin is a polymer of 1,1-bis(trifluoromethyl)butadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate. (i) First, the proportions (molar ratios) of each component are calculated by NMR determination of the fluorinated resin. (ii) Multiply the molecular weight (Mw) of each monomer in the fluorinated resin by its molar ratio, add the results together, and calculate the total value. Calculate the weight ratio (wt%) of each component from this total value. In addition, 1,1-bis(trifluoromethyl)butadiene has a molecular weight of 190, 4-hydroxystyrene has a molecular weight of 120, and 2-(perfluorohexyl)ethyl methacrylate has a molecular weight of 432. (iii) Next, in the fluorine-containing composition, the fluorine content in the monomer is calculated. (iv) Calculate the "fluorine content in monomers ÷ monomer molecular weight (Mw) × weight ratio (wt%)" for each component, and add the obtained values ​​together. (v) Calculate the fluorine atom content of the fluorine-containing resin by calculating the ratio of the value obtained in (iv) above to the total value obtained in (ii) above.

[0041] In the fluorinated resin of the present invention, preferably at least a portion of the monomer (A) has the structure represented by the following formula (1) or formula (1'). CH2=C(R 1 )C≡CR 2 …(1) CH2=C(R 1 )XC≡CR 2 …(1') In equations (1) and (1'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R 2 The alkyl group refers to a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.

[0042] Furthermore, in the fluorinated resin of the present invention, the structure represented by the above formula (1) or (1') is preferably the structure represented by the following formula (2) or formula (2'). CH2=C(R 1 )C≡CR f …(2) CH2=C(R 1 )XC≡CR f …(2') In equations (2) and (2'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to a straight-chain perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.

[0043] As preferred structures of equations (1) and (1') (including preferred structures of equations (2) and (2'), the structures represented by equations (1-1) to (1-4) and (2-1) to (2-4) can be listed below.

[0044] CH2=CHC≡CCF2H…(1-1) CH2=CHC≡CC2F4H…(1-2) CH2=C(CH3)C≡CCF2H…(1-3) CH2=C(CH3)C≡CC2F4H…(1-4) CH2=CHC≡CCF3…(2-1) CH2=CHC≡CC4F9…(2-2) CH2=C(CH3)C≡CCF3…(2-3) CH2=C(CH3)C≡CC4F9…(2-4)

[0045] Furthermore, in the fluorinated resin of the present invention, the repeating unit (U) preferably comprises the above-mentioned monomer (A) and a monomer (B) having the structure represented by the following formula (3) or formula (3') as a monomer unit.

[0046] CH2=C(R 1 COOR 2 …(3) CH2=C(R 1 COOXR 2 …(3') In equations (3) and (3'), R 1Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R 2 The alkyl group refers to a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.

[0047] Furthermore, as the monomer represented by formula (3) and formula (3'), it is preferable to have the structure represented by the following formula (4) and formula (4').

[0048] CH2=C(R 1 COOR f …(4) CH2=C(R 1 COOXR f …(4') In equations (4) and (4'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, indicating a straight-chain alkylene group with 1 to 10 carbon atoms, a branched alkylene group with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to a straight-chain perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.

[0049] As a more preferred structure of equations (4) and (4'), the following structures (4'-1) to (4'-3) can be listed.

[0050] CH2=C(CH3)COOC2H4C6F 13 …(4'-1) CH2=C(CH3)COOC2H4C4F9…(4'-2) CH2=C(CH3)COOCH(CF3)CF3…(4'-3)

[0051] When the repeating unit (U) of the fluorinated resin of the present invention comprises two or more different types of structures represented by formulas (1), (1'), (2), (2'), (3), (3'), (4), and (4'), in each structure, R 1 R 2 R f X can be the same or different.

[0052] In the fluorinated resin of the present invention, it is preferable that at least a portion of the side chains of the monomer (A) contain fluorine atoms. Furthermore, the fluorine atom can be positioned as a side chain in the structures shown in formula (1), formula (1'), formula (2) or formula (2'), or it can be positioned as a side chain in other structures.

[0053] In the fluorinated resin of the present invention, preferably at least a portion of the triple bond is a carbon-nitrogen triple bond of a cyano group. Furthermore, the fluorine atom can be positioned as a side chain in the structures shown in formula (1), formula (1'), formula (2) or formula (2'), or it can be positioned as a side chain in other structures.

[0054] The molecular weight of the fluorinated resin of the present invention 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, based on the mass-average molecular weight obtained by gel permeation chromatography (GPC) using polystyrene as a standard. If the molecular weight is less than 1,000, there is a tendency for the strength of the formed fluorinated resin film or organic EL barrier to decrease. If the molecular weight is greater than 1,000,000, the solubility in the solvent is insufficient, and it may become difficult to form a fluorinated resin film by coating.

[0055] The distribution index (Mw / Mn) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

[0056] The fluorinated resin of the present invention can be used in liquid repellents or photosensitive resin compositions.

[0057] (Photosensitive resin composition) The photosensitive resin composition of the present invention is characterized in that it comprises at least the fluorinated resin, solvent and photopolymerization initiator of the present invention described above.

[0058] The photosensitive resin composition of the present invention can be used to form dams (separation walls). Because it contains the fluorinated resin of the present invention described above, a barrier (partition wall) with sufficiently high liquid repellency can be produced. Furthermore, the liquid repellency of the produced barrier (partition wall) does not easily decrease even after UV ozone treatment or oxygen plasma treatment.

[0059] The solvent contained in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve the fluorinated resin, and examples include ketones, alcohols, polyols and their derivatives, ethers, esters, aromatic solvents, fluorinated solvents, etc. These solvents can be used alone or in combination of two or more.

[0060] Specifically, examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. As alcohols, specifically, examples include isopropanol, butanol, isobutanol, n-pentanol, isoamyl alcohol, tert-amyl alcohol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, sec-amyl alcohol, tert-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, oleyl alcohol, etc.

[0061] As polyols and their derivatives, specific examples include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), and monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0062] As ethers, specific examples include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0063] As esters, specific examples 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.

[0064] Examples of fluorinated solvents include Freon, chlorofluorocarbon substitutes, perfluorinated compounds, and hexafluoroisopropanol.

[0065] In addition, to improve coatability, turpentine-based naphtha solvents or paraffin-based solvents, which are high-boiling-point weak solvents, can be used.

[0066] The solvent is preferably selected from at least one of the following groups: methyl ethyl ketone, cyclohexanone, methyl isopentyl 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 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 hexafluoroisopropanol. More preferably, it is selected from at least one of the group consisting of methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate and γ-butyrolactone.

[0067] Relative to 100 parts by mass of the concentration of the fluorinated resin (wherein, when the photosensitive resin composition contains an alkali-soluble resin described later, the concentration includes that resin), the amount of solvent in the photosensitive resin composition of the present invention is preferably in the range of 50 parts by mass to 2,000 parts by mass. More preferably, it is 100 parts by mass to 1,000 parts by mass. By adjusting the amount of solvent, the film thickness of the formed resin film can be adjusted. If the amount of solvent is within the above range, a film thickness particularly suitable for obtaining a barrier for organic EL can be obtained.

[0068] The photopolymerization initiator contained in the photosensitive resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator that polymerizes monomers with polymerizable double bonds by high-energy rays such as electromagnetic waves or electron beams, and known photopolymerization initiators can be used. As photopolymerization initiators, photoradical initiators or photoacid initiators can be used. These photopolymerization initiators can be used alone, or simultaneously with photoradical initiators and photoacid initiators, or in combination of two or more photoradical initiators or photoacid initiators. In addition, living polymerization can be carried out by using additives while using photopolymerization initiators, depending on the situation. Well-known additives can be used.

[0069] Specifically, photoradical initiators can be classified into two types: intramolecular cleavage initiators, which generate free radicals by breaking intramolecular bonds through the absorption of electromagnetic waves or electron beams; and hydrogen abstraction initiators, which generate free radicals by simultaneously using hydrogen donors such as tertiary amines or ethers. Either type can be used. Photoradical initiators other than those listed above can also be used.

[0070] Specifically, photoradical initiators include benzophenone, acetophenone, diketone, acylphosphine oxide, quinone, and acyloin.

[0071] Specifically, examples of benzophenone-based compounds include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0072] Specifically, 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0073] As diketone compounds, examples include 4,4'-dimethoxybenzoiloyl, methyl benzoylformate, and 9,10-phenanthroquinone. Among these, 4,4'-dimethoxybenzoiloyl and methyl benzoylformate are preferred.

[0074] As an acylphosphine oxide system, examples include phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, etc.

[0075] As quinones, examples include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Camphorquinone and 1,4-naphthoquinone are preferred.

[0076] As an alcohol-ketone system, specifically, examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

[0077] As a photoradical initiator, benzophenone-based, acetophenone-based, and diketone-based initiators are preferred, with benzophenone-based initiators being more preferred.

[0078] Preferred photoradical initiators among commercially available photoradical initiators include those manufactured by BASF Corporation: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, Lucirin TPO, etc. Among these, Irgacure 651 and Irgacure 369 are preferred.

[0079] Specifically, the photoinitiator is an onium salt composed of a pair of cations and anions, wherein the cation is at least one selected from the group consisting of aromatic sulfonic acids, aromatic iodonium, aromatic diazo, aromatic ammonium, thiaanthenium, thioxanone onium, and (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and the anion is at least one selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. Among them, bis[4-(diphenylsulfonium)phenyl]sulfide-bis(hexafluorophosphate), bis[4-(diphenylsulfonium)phenyl]sulfide-tetra(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0080] Commercially available photoinitiators include: San-Apro Ltd.'s CPI-100P, CPI-110P, CPI-101A, CPI-200K, and CPI-210S; Dow Chemical Japan Limited's Cyracure UVI-6990, Cyracure UVI-6992, and Cyracure UVI-6976; ADEKA CORPORATION's Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, and Adeka Optomer SP-300; Nippon Soda Co., Ltd.'s CI-5102 and CI-2855; and SANSHIN CHEMICAL INDUSTRY Co., Ltd.'s 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's Esacure 1064, Esacure 1187; BASF's Irgacure 250, etc.

[0081] Relative to 100 parts by weight of the fluorinated resin (wherein, when the photosensitive resin composition contains an alkali-soluble resin described later, the concentration includes that resin), the content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably 0.1 parts by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 20 parts by weight or less. If the content of the photopolymerization initiator is less than 0.1 parts by weight, there is a tendency to not be able to obtain a sufficient crosslinking effect; if it exceeds 30 parts by weight, there is a tendency to decrease the resolution or sensitivity.

[0082] In addition to fluorinated resin, solvent and photopolymerization initiator as essential components, the photosensitive resin composition of the present invention may also include crosslinking agent, alkali-soluble resin, naphthoquinone diazide compound, basic compound and other additives.

[0083] The crosslinking agent contained in the photosensitive resin composition of the present invention can react with the repeating unit (U) of the fluorinated resin to make the resin crosslinked, thereby improving the mechanical strength of the formed film.

[0084] Known crosslinking agents can be used. Specifically, examples include: compounds formed by reacting formaldehyde or formaldehyde and lower alcohols with amino-containing compounds such as melamine, methylguanidine, benzoguanidine, urea, ethylene urea, acrylurea, and glycourea, and replacing the hydrogen atom of the amino group with hydroxymethyl or lower alkoxymethyl groups; polyfunctional epoxy compounds; polyfunctional oxetane compounds; polyfunctional isocyanate compounds; and polyfunctional acrylate compounds. Here, crosslinking agents using melamine are referred to as melamine-based crosslinking agents, those using urea are referred to as urea-based crosslinking agents, those using alkylene urea such as ethylene urea and acrylurea are referred to as alkylene urea-based crosslinking agents, and those using glycourea are referred to as glycourea-based crosslinking agents. These crosslinking agents can be used alone or in combination of two or more.

[0085] As a crosslinking agent, it is preferably selected from at least one of these crosslinking agents, with glycourea-based crosslinking agents and polyfunctional acrylate compounds being particularly preferred.

[0086] Examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine, among which hexamethoxymethyl melamine is preferred.

[0087] Examples of urea-based crosslinking agents include dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, among which dimethoxymethylurea is preferred.

[0088] Examples of alkylene urea crosslinking agents include mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, mono- and / or dibutoxymethylated ethylene urea, etc.; mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, mono- and / or dibutoxymethylated propylene urea, etc.; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0089] Examples of glycourea-based crosslinking agents include mono-, di-, tri-, and / or tetra-hydroxymethylated glycourea; mono-, di-, tri-, and / or tetra-methoxymethylated glycourea; mono-, di-, tri-, and / or tetra-ethoxymethylated glycourea; mono-, di-, tri-, and / or tetra-propoxymethylated glycourea; and mono-, di-, tri-, and / or tetra-butoxymethylated glycourea.

[0090] Examples of polyfunctional acrylate compounds include polyfunctional acrylates (e.g., products manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP), polyethylene glycol diacrylates (e.g., products manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.: A-200, A-400, A-600), urethane acrylates (e.g., products manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), pentaerythritol tetraacrylates, etc.

[0091] The following examples illustrate preferred polyfunctional acrylate compounds.

[0092] [Chemical Formula 1]

[0093] [Chemical Formula 2]

[0094] [Chemical Formula 3]

[0095] Relative to 100 parts by weight of the fluorinated resin (wherein, when the photosensitive resin composition includes an alkali-soluble resin described later, the concentration includes that resin), the content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 10 parts by weight or more and 300 parts by weight or less, more preferably 50 parts by weight or more and 200 parts by weight or less. If the content of the crosslinking agent is less than 10 parts by weight, there is a tendency to not be able to obtain a sufficient crosslinking effect; if it exceeds 300 parts by weight, there is a tendency to decrease the resolution or sensitivity.

[0096] If the photosensitive resin composition of the present invention contains an alkali-soluble resin, the dam obtained from the photosensitive resin composition of the present invention can have a good shape.

[0097] Alkali-soluble resins include alkali-soluble phenolic varnish resins. Alkali-soluble phenolic varnish resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

[0098] Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, pyrogallol, thymol, carvacrol, etc. These phenols can be used alone or in combination of two or more.

[0099] Specifically, examples of aldehydes include formaldehyde, paraformaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts can be used alone or in combination of two or more.

[0100] Furthermore, acid-modified epoxy acrylate resins can be listed as alkali-soluble resins. Commercially available acid-modified epoxy acrylate resins include, for example, those manufactured by NIPPON KAYAKU Co., Ltd., under the following 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.

[0101] From the perspective of the developability and resolution of the photosensitive resin composition, the mass-average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000.

[0102] The content of alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 500 parts by weight or more and 10,000 parts by weight or less, more preferably 1,000 parts by weight or more and 7,000 parts by weight or less, relative to 100 parts by weight of the fluorinated resin. If the content of alkali-soluble resin exceeds 10,000 parts by weight, there is a tendency that the ink-repellent properties of the fluorinated resin of the present invention, after UV ozone treatment or oxygen plasma treatment, cannot be sufficiently obtained.

[0103] If the photosensitive resin composition of the present invention contains a naphthoquinone diazido group compound, the dam obtained from the photosensitive resin composition of the present invention can have a good shape. There are no particular restrictions on naphthoquinone diazido compounds; naphthoquinone diazido compounds that are commonly used as photosensitive components in photoresist compositions for i-line applications can be used.

[0104] Examples of naphthoquinone-containing diazidoyl compounds include naphthoquinone-1,2-diazido-4-sulfonate compounds, naphthoquinone-1,2-diazido-5-sulfonate compounds, naphthoquinone-1,2-diazido-6-sulfonate compounds, naphthoquinone-1,2-diazido-sulfonate compounds, o-benzoquinone diazido-sulfonate compounds, and o-anthraquinone diazido-sulfonate compounds. Among these, naphthoquinone-1,2-diazido-4-sulfonate compounds, naphthoquinone-1,2-diazido-5-sulfonate compounds, and naphthoquinone-1,2-diazido-6-sulfonate compounds are preferred due to their excellent solubility. These compounds can be used alone or in combination of two or more.

[0105] Relative to 100 parts by weight of the fluorinated resin (wherein, when the photosensitive resin composition includes the above-mentioned alkali-soluble resin, the concentration includes the resin), the content of the naphthoquinone diazido compound in the photosensitive resin composition of the present invention is preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight. If it exceeds 60 parts by weight, there is a tendency to make it difficult to obtain the sensitivity of the photosensitive resin composition.

[0106] If the photosensitive resin composition of the present invention contains an alkaline compound, it has the effect of slowing down the diffusion rate of the acid generated by the above-mentioned photoacid generator into the film of the photosensitive resin composition of the present invention. By incorporating alkaline compounds, the acid diffusion distance can be adjusted, thus ensuring a good shape for the dike. Furthermore, by incorporating alkaline compounds, even with a long postexposure delay time from the formation of the barrier to exposure, the barrier is not easily deformed and can be stably formed to the required precision.

[0107] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Aliphatic amines are preferred, specifically including aliphatic secondary or tertiary amines and alkyl alcohol amines. These basic compounds can be used alone or in combination of two or more.

[0108] As aliphatic amines, alkylamines or alkylolamines can be listed as those in which at least one hydrogen atom of ammonia (NH3) is replaced by an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples 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-decylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-nonylamine, di-n-decylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-octanolamine. Among them, dialkylamines, trialkylamines, and alkylolamines are preferred, and alkylolamines are more preferred. Among alkylolamines, triethanolamine and triisopropanolamine are particularly preferred.

[0109] Examples of aromatic and heterocyclic amines include 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 derivatives; 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- Heterocyclic amines such as dimethylimidazoline; hindered amines such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; nitrogen-containing alcohols such as 2-hydroxypyridine, carbamophenol, 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, and 1-[2-(2-hydroxyethoxy)ethyl]piperazine; methylpyridine, dimethylpyridine, pyrrole, piperidine, piperazine, indole, and hexamethylenetetramine.

[0110] In the photosensitive resin composition of the present invention, the content of the alkaline compound is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the fluorinated resin (wherein, when the photosensitive resin composition includes the above-mentioned alkali-soluble resin, the concentration includes the resin). If the amount of alkaline compound is less than 0.001 parts by mass, it is difficult to obtain sufficient effect as an additive; if it exceeds 2 parts by mass, there is a tendency for a decrease in resolution or sensitivity.

[0111] The photosensitive resin composition of the present invention may also contain other additives as needed. Examples of other additives include dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, defoamers, compatibilizers, sealing agents, antioxidants, and many others. These other additives may be well-known additives.

[0112] In addition, as a surfactant, it is preferred to contain one or more of fluorinated or silicone surfactants (fluorinated surfactants and silicone surfactants, surfactants containing both fluorine and silicon atoms).

[0113] Next, a method for forming a partition wall using the photosensitive resin composition of the present invention will be described. The method for forming the partition wall may include: (1) a film forming process, (2) an exposure process and (3) a development process. The following is a description of each process.

[0114] (1) Film forming process First, the photosensitive resin composition of the present invention is coated onto a substrate and then heated to form a fluorinated resin film. There are no particular limitations on the heating conditions, but 80–100°C and 60–200 seconds are preferred. This allows for the removal of solvents and other contaminants from the photosensitive resin composition.

[0115] As a substrate, silicon wafers, metals, glass, ITO substrates, etc. can be used. Furthermore, organic or inorganic films can be pre-formed on the substrate. For example, an anti-reflective film, a multilayer resist substrate, or a pattern can be formed on it. Additionally, the substrate can be pre-cleaned. For example, it can be cleaned using ultrapure water, acetone, or alcohols (methanol, ethanol, isopropanol).

[0116] As a method for coating the photosensitive resin composition of the present invention onto a substrate, known methods such as spin coating can be used.

[0117] (2) Exposure process Next, the required photomask is placed in the exposure device, and the fluorinated resin film is exposed to high-energy rays through the photomask. The high-energy rays are preferably selected from at least one of the group consisting of ultraviolet rays, gamma rays, X-rays and alpha rays.

[0118] The preferred exposure dose for high-energy rays is 1 mJ / cm. 2 Above 200mJ / cm 2 The following is more preferably 10 mJ / cm 2 Above 100mJ / cm 2 the following.

[0119] (3) Developing process Next, the fluorinated resin film after the exposure process is developed with an alkaline aqueous solution to produce a fluorinated resin patterned film. That is, a fluoropolymer patterned film is made by dissolving either the exposed or unexposed portion of the fluoropolymer film in an alkaline aqueous solution.

[0120] As an alkaline aqueous solution, tetramethylammonium hydroxide (TMAH) aqueous solution, tetrabutylammonium hydroxide (TBAH) aqueous solution, etc. 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, more preferably 2% by mass or more and 3% by mass or less.

[0121] The developing method can be any known method, such as immersion developing, rotary immersion developing, spray developing, etc.

[0122] The development time (the contact time between the developer and the fluorinated resin film) is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.

[0123] After development, a cleaning step using deionized water or similar methods to clean the fluorinated resin pattern film may be included as needed. The cleaning method and time are preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.

[0124] Partitions manufactured in this way can be used as partitions for displays.

[0125] The display of the present invention is characterized by comprising a light-emitting element, the light-emitting element comprising: a partition wall formed of the photosensitive resin composition of the present invention described above; and a light-emitting layer disposed in the region divided by the partition wall. Examples of displays include organic EL displays and quantum dot displays. Example

[0126] The present invention will be described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0127] 1. Synthesis of monomers [Synthetic Example 1] Synthesis of 5,5,5-trifluoro-2-methyl-1-penten-3-yne (TFMPY) Add 13 g of trans-1-chloro-3,3,3-trifluoropropene (product name: 1233E, manufactured by Central Glass Co., Ltd.) and 50 mL of tetrahydrofuran to a 500 mL glass flask equipped with a stirrer, and cool to -78 °C. Add 100 mL of 1.6 M hexane solution of n-butyllithium dropwise, stir for 30 minutes, then add 5.81 g of dehydrated acetone. After stirring for 1 hour, add 100 mL of water to separate the organic layer. Repeat the washing of the separated organic layer with 100 mL of water three times, then recover the fraction at 99–103 °C by atmospheric distillation to obtain 10.5 g of 5,5,5-trifluoro-2-methyl-3-pentyn-2-ol (hereinafter referred to as TFMPO) in 69% yield.

[0128] [Chemical Formula 4] Next, 15g of concentrated sulfuric acid was added to a 100ml glass flask equipped with a stirrer, and the mixture was heated to 100°C. Then, 10g of TFMPO was slowly added dropwise over one hour. After the addition was complete, the mixture was stirred at 100°C for 60 minutes. 19 F-NMR analysis of the reaction solution revealed no residual feedstock. Subsequently, the fraction at 68–70 °C was recovered from the reaction solution by atmospheric distillation to obtain 5,5,5-trifluoro-2-methyl-1-penten-3-yne (hereinafter referred to as TFMPY) in 55% yield.

[0129] [Chemical Formula 5]

[0130] <NMR Analysis Results> 1 ¹H-NMR (solvent: deuterated chloroform, internal standard: TMS); δ (ppm) 1.92 (¹H, m), 5.52 (¹H, m), 5.85 (¹H, m) 19 F-NMR (solvent: deuterated chloroform, internal standard: C6D6); δ (ppm) -49.8 (3F, S)

[0131] [Synthetic Example 2] Synthesis of 4-hydroxystyrene (p-HO-St) (Synthesized with reference to the embodiment described in Japanese Patent Application Publication No. 2016-98181) At room temperature (approximately 20°C), 100 g of 4-acetoxystyrene (a product of TOKYOCHEMICAL INDUSTRY CO., LTD.; hereinafter referred to as p-AcO-St) and 300 g of methanol were mixed in a 1000 ml glass flask equipped with a stirrer. 0.50 g (equivalent to 0.5% by mass of p-AcO-St) of 1,3,5-trihydroxybenzene as a polymerization inhibitor was added. The solution was then cooled to 0°C in an ice bath, and a 12% by mass aqueous solution of sodium hydroxide (equivalent to 1.0 equivalent of p-AcO-St) was slowly added dropwise over 40 minutes, followed by stirring at 0°C for 30 minutes. 1 H-NMR analysis of the reaction solution revealed no residual starting material. Next, an 18% hydrochloric acid aqueous solution (equivalent to 0.8 equivalents of p-AcO-St) was added dropwise over 30 minutes, followed by stirring for 30 minutes after the addition. The pH of the solution was measured and found to be 6. The resulting reaction solution was extracted with 360 g of methyl tert-butyl ether at room temperature (approximately 20°C). The solution was then washed twice with 330 g of purified water. 1,3,5-Trihydroxybenzene was added to the obtained organic layer at 1% by mass of 4-hydroxystyrene. The 4-hydroxystyrene was then concentrated to 72% by mass and added to n-octane, a poor solvent, cooled to 0°C. The solution was then immersed in an ice bath and stirred for 1 hour, causing 4-hydroxystyrene crystals to precipitate. The crystals were filtered and further washed with n-octane. Next, the crystals were dried at 25°C under reduced pressure to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield 66%).

[0132] [Chemical Formula 6]

[0133] 2. Manufacturing of fluorinated resins (First step: Polymerization) [Determination of the molar ratio of monomers constituting each repeating unit] NMR according to 1 H-NMR, 19 F-NMR or 13 C-NMR measurements determine the molar ratio of monomers that make up each repeating unit in the polymer.

[0134] [Determination of polymer molecular weight] GPC The weight-average molecular weight (Mw) and molecular weight distribution index (the ratio of number-average molecular weight (Mn) to weight-average molecular weight (Mw); Mw / Mn) of the polymer were determined using a high-performance gel permeation chromatography (GPC; manufactured by TOSOH CORPORATION, model HLC-8320GPC). ALPHA-M columns and ALPHA-2500 columns (both manufactured by TOSOH CORPORATION) were connected in series one by one, and tetrahydrofuran (THF) was used as the developing solvent. A refractive index difference detector was used.

[0135] 2-1. Polymerization of fluorinated resin precursors Synthesis of Fluorine Resin Precursor 1 At room temperature (approximately 20°C), weigh 10.6 g (0.2 mol) of acrylonitrile (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as AN), 49.8 g (0.15 mol) of 2-(perfluorobutyl)ethyl methacrylate (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as MA-C4F), 19.5 g (0.15 mol) of 2-hydroxyethyl methacrylate (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as HEMA), and 80 g of methyl ethyl ketone (hereinafter referred to as MEK) into a 500 ml glass flask equipped with a stirrer. Add 1.6 g (0.01 mol) of 2,2'-azobis(2-methylbutyronitrile) (TOKYO CHEMICAL INDUSTRY CO.,LTD.). The product of CO.,LTD. (hereinafter referred to as AIBN) was degassed while stirring, then the flask was purged with nitrogen, and the temperature was raised to 75°C. The reaction was carried out for 6 hours. 400 g of n-heptane was added dropwise to the reaction system, resulting in the precipitation of a transparent, viscous substance. This viscous substance was separated by decantation. It was dried under reduced pressure at 60°C to obtain 69 g of the fluorinated resin precursor 1 as the transparent viscous substance in 86% yield.

[0136] <NMR Measurement Results> The composition ratio of repeating units in the fluorinated resin precursor 1, expressed in mole percent, is: monomer units from AN : monomer units from MA-C4F : monomer units from HEMA = 41 : 28 : 31.

[0137] [Chemical Formula 7]

[0138] <GPC Measurement Results> Mw = 6,700, Mw / Mn = 1.3

[0139] Synthesis of Fluorine Resin Precursor 2 Except that 2-(perfluorohexyl)ethyl methacrylate (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as MA-C6F) was used instead of MA-C4F, the fluorinated resin precursor 2, comprising the following repeating units, was obtained in 85% yield by the same steps as the synthesis of fluorinated resin precursor 1.

[0140] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 2, expressed in mole percent, is: monomer unit from AN : monomer unit from MA-C6F : monomer unit from HEMA = 42 : 27 : 31.

[0141] [Chemical Formula 8]

[0142] <GPC Measurement Results> Mw = 6,300, Mw / Mn = 1.3

[0143] Synthesis of Fluorine Resin Precursor 3 Except that methacrylonitrile (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as MN) was used instead of AN, the fluorinated resin precursor 3, comprising the following repeating units, was obtained in 83% yield by the same steps as the synthesis of the fluorinated resin precursor 1.

[0144] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 3, expressed in mole percent, is: monomer unit from MN : monomer unit from MA-C4F : monomer unit from HEMA = 40 : 28 : 32.

[0145] [Chemical Formula 9]

[0146] <GPC Measurement Results> Mw = 4,700, Mw / Mn = 1.3

[0147] Synthesis of Fluorine Resin Precursor 4 Except for using MN instead of AN, the fluorinated resin precursor 4, which contains the following repeating units, was obtained in 83% yield by following the same steps as the synthesis of the fluorinated resin precursor 2.

[0148] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 4, expressed in mole percent, is: monomer unit from MN : monomer unit from MA-C6F : monomer unit from HEMA = 39 : 29 : 32.

[0149] [Chemical Formula 10]

[0150] <GPC Measurement Results> Mw = 4,200, Mw / Mn = 1.3

[0151] Synthesis of Fluorine Resin Precursor 5 Except that TFMPY obtained in Synthesis Example 1 was used instead of AN, fluorinated resin precursor 5 containing the following repeating units was obtained in 80% yield by following the same steps as the synthesis of fluorinated resin precursor 3-1.

[0152] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 5, expressed in mole percent, is 38:30:32 for monomer units from TFMPY: 30:30 for monomer units from MA-C4F.

[0153] [Chemical Formula 11]

[0154] <GPC Measurement Results> Mw = 4,400, Mw / Mn = 1.3

[0155] Synthesis of Fluorine Resin Precursor 6 Except that TFMPY obtained in Synthesis Example 1 was used instead of AN, fluorinated resin precursor 6 containing the following repeating units was obtained in 81% yield by following the same steps as the synthesis of fluorinated resin precursor 2.

[0156] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 6, expressed in mole percent, is: monomer unit from TFMPY : monomer unit from MA-C6F : monomer unit from HEMA = 39 : 29 : 32.

[0157] [Chemical Formula 12]

[0158] <GPC Measurement Results> Mw = 4,600, Mw / Mn = 1.3

[0159] Synthesis of Fluorine Resin Precursor 7 At room temperature (approximately 20°C), 10.6 g (0.2 mol) of AN, 49.8 g (0.15 mol) of MA-C4F, 19.5 g (0.15 mol) of HEMA, 8.66 g (0.1 mol) of methacrylic acid (hereinafter referred to as MAA), and 89 g of MEK were weighed into a 500 ml glass flask equipped with a stirrer. 1.6 g (0.01 mol) of AIBN was added, and the mixture was degassed while stirring. The flask was then purged with nitrogen, and the temperature was raised to 75°C. The reaction was allowed to proceed for 6 hours. 450 g of n-heptane was added dropwise to the reaction system, resulting in the precipitation of a transparent, viscous substance. This viscous substance was separated by decantation. The substance was dried under reduced pressure at 60°C, yielding 74 g of the fluorinated resin precursor 7 as the transparent viscous substance in 84% yield.

[0160] <NMR Measurement Results> The composition ratio of repeating units in the fluorinated resin precursor 7, expressed in mole percent, is: monomer units from AN : monomer units from MA-C4F : monomer units from HEMA : monomer units from MAA = 33 : 24 : 26 : 17.

[0161] [Chemical Formula 13]

[0162] <GPC Measurement Results> Mw = 7,700, Mw / Mn = 1.4

[0163] Synthesis of Fluorine Resin Precursor 8 Except for using MN instead of AN and using MA-C6F instead of MA-C4F, the fluorinated resin precursor 8, which contains the following repeating units, was obtained in 81% yield by following the same steps as the synthesis of the fluorinated resin precursor 7.

[0164] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 8, expressed in mole percent, is: monomer unit from MN : monomer unit from MA-C6F : monomer unit from HEMA : monomer unit from MAA = 34 : 23 : 25 : 18.

[0165] [Chemical Formula 14]

[0166] <GPC Measurement Results> Mw = 5,300, Mw / Mn = 1.3

[0167] Synthesis of Fluorine Resin Precursor 9 Except for using MA-C6F instead of MA-C4F and acrylic acid (hereinafter referred to as AA) instead of MAA, the fluorinated resin precursor 9 containing the following repeating units was obtained in 81% yield by the same steps as the synthesis of the fluorinated resin precursor 7.

[0168] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 9, expressed in mole percent, is: monomer unit from AN : monomer unit from MA-C6F : monomer unit from HEMA : monomer unit from AA = 34 : 23 : 27 : 16.

[0169] [Chemical Formula 15]

[0170] <GPC Measurement Results> Mw = 6,900, Mw / Mn = 1.3

[0171] Synthesis of Fluorine Resin Precursor 10 Except for using MN instead of AN and AA instead of MAA, the fluorinated resin precursor 10, containing the following repeating units, was obtained in 82% yield by following the same steps as the synthesis of the fluorinated resin precursor 7.

[0172] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 10, expressed in mole percent, is: monomer unit from MN : monomer unit from MA-C4F : monomer unit from HEMA : monomer unit from AA = 33 : 24 : 26 : 17.

[0173] [Chemical Formula 16]

[0174] <GPC Measurement Results> Mw = 5,500, Mw / Mn = 1.3

[0175] 2-2. Comparison of the synthesis of fluorinated resin precursors [Comparison Aggregation Example 1] At room temperature (approximately 20°C), 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of hexafluoroisopropyl methacrylate (manufactured by Central Glass Co., Ltd., hereinafter referred to as HFIP-M), 17.32 g (0.2 mol) of MAA, and 84 g of MEK were weighed into a 300 ml glass flask equipped with a stirrer, and 1.6 g (0.010 mol) of AIBN was added. Degassing was performed while stirring, followed by purging with nitrogen. The mixture was heated to 80°C and reacted for 6 hours. The reaction mixture was then added dropwise to 500 g of n-heptane, resulting in a white precipitate. The precipitate was filtered and dried under reduced pressure at 60°C to obtain 55 g of a comparative fluoropolymer precursor 1 as a white solid, in a yield of 64%.

[0176] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 1, expressed as a molar ratio, is: monomer unit from MA-C6F : monomer unit from HFIP-M : monomer unit from MAA = 26 : 20 : 54.

[0177] [Chemical Formula 17]

[0178] <GPC Measurement Results> Mw = 9,700, Mw / Mn = 1.5

[0179] [Comparison Aggregation Example 2] 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 HFIP-M, 8.66 g (0.1 mol) of MAA, and 88 g of MEK were weighed into a 300 ml glass flask equipped with a stirrer, and 1.6 g (0.010 mol) of AIBN was added. The mixture was degassed while stirring, and then the flask was purged with nitrogen. The mixture was heated to 80 °C and reacted for 6 hours. The reaction solution was then added dropwise to 500 g of n-heptane, resulting in a white precipitate. The precipitate was filtered and dried under reduced pressure at 60 °C to obtain 60 g of a comparative fluorinated resin precursor 2 as a white solid in a yield of 68%.

[0180] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 2, expressed as a molar ratio, is: monomer unit from HEMA : monomer unit from MA-C6F : monomer unit from HFIP-M : monomer unit from MAA = 24 : 26 : 24 : 26.

[0181] [Chemical Formula 18]

[0182] <GPC Measurement Results> Mw = 10,700, Mw / Mn = 1.5

[0183] [Comparison Aggregation Example 3] At room temperature, 12.2 g (0.10 mol) of p-HO-St obtained in Synthesis Example 2, 43.2 g (0.1 mol) of MA-C6F, 8.8 g (0.1 mol) of 2-hydroxyethyl vinyl ether (a product of TOKYOCHEMICAL INDUSTRY CO.,LTD.; hereinafter referred to as HEVE), and 64 g of MEK were weighed into a 300 ml glass flask equipped with a stirrer, and 1.6 g (0.010 mol) of AIBN was added. The mixture was degassed while stirring, and then the flask was purged with nitrogen. The temperature was raised to 80 °C and the reaction was carried out for 6 hours. The reaction solution was added dropwise to 500 g of n-heptane, resulting in a white precipitate. The precipitate was filtered and dried under reduced pressure at 60 °C to obtain 51 g of comparative fluorinated resin precursor 3 as a white solid in 81% yield.

[0184] <NMR Measurement Results> The composition ratio of each repeating unit of the fluorinated resin precursor 3, expressed as a molar ratio, is: monomer unit from HEVE : monomer unit from MA-C6F : monomer unit from p-HO-St = 35 : 31 : 34.

[0185] [Chemical Formula 19]

[0186] <GPC Measurement Results> Mw = 17,300, Mw / Mn = 1.7

[0187] 3. Manufacturing of fluorinated resins (Second step: Addition reaction) Fluorinated resins were synthesized by reacting fluorinated resin precursors 1-6 obtained in "2. Manufacturing of Fluorinated Resins (First Step: Polymerization)" with acrylic acid derivatives. Karenz-AOI (a product of ShowaDenko KK) was used as the acrylic acid derivative. The reaction was an addition reaction between the hydroxyl groups in each fluorinated resin precursor and the acrylic acid derivative.

[0188] [Chemical Formula 20]

[0189] [Synthesis of Fluorine Resin 1] 10 g (0.019 mol hydroxyl equivalent) of fluorinated resin precursor 1 and 20 g of PGMEA were weighed into a 300 ml glass flask equipped with a stirrer, and 2.68 g (0.019 mol) of Karenz-AOI was added. The mixture was reacted at 45 °C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 150 g of n-heptane was added to precipitate the precipitate. The precipitate was filtered and dried under reduced pressure at 40 °C to obtain 11.4 g of fluorinated resin 1 as a white solid in 90% yield.

[0190] < 13 C-NMR measurement results > In fluorinated resin 1, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from AN, monomer unit from MA-C4F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 1 used (same as before the introduction of the crosslinking group).

[0191] Synthesis of Fluorine-Containing Resin 2 Except that fluorinated resin precursor 2 is used instead of fluorinated resin precursor 1, fluorinated resin 2 is obtained in 91% yield by the same steps as the synthesis of fluorinated resin 1.

[0192] < 13 C-NMR measurement results > In fluorinated resin 2, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 95:5. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from AN, monomer unit from MA-C6F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 2 used (same as before the introduction of the crosslinking group).

[0193] Synthesis of Fluorine-Containing Resin 3 Except that fluorinated resin precursor 3 is used instead of fluorinated resin precursor 1, fluorinated resin 3 is obtained in 90% yield by the same steps as the synthesis of fluorinated resin 1.

[0194] < 13 C-NMR measurement results > In fluorinated resin 3, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 97:3. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MN, monomer unit from MA-C4F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 3 used (same as before the introduction of the crosslinking group).

[0195] Synthesis of Fluorine-Containing Resin 4 Except that fluorinated resin precursor 4 is used instead of fluorinated resin precursor 1, fluorinated resin 4 is obtained in 89% yield by the same steps as the synthesis of fluorinated resin 1.

[0196] < 13 C-NMR measurement results > In fluorinated resin 4, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MN, monomer unit from MA-C6F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 4 used (same as before the introduction of the crosslinking group).

[0197] Synthesis of Fluorine-Containing Resin 5 Except that fluorinated resin precursor 5 is used instead of fluorinated resin precursor 1, fluorinated resin 5 is obtained in 92% yield by the same steps as the synthesis of fluorinated resin 1.

[0198] < 13 C-NMR measurement results > In fluorinated resin 5, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 95:5. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from TFMPY and monomer unit from MA-C4F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 5 used (same as before the introduction of the crosslinking group).

[0199] Synthesis of Fluorine-Containing Resin 6 Except that fluorinated resin precursor 6 is used instead of fluorinated resin precursor 1, fluorinated resin 6 is obtained in 89% yield by the same steps as the synthesis of fluorinated resin 1.

[0200] < 13 C-NMR measurement results > In fluorinated resin 6, the molar ratio of the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) is 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from TFMPY and monomer unit from MA-C6F) that does not react with the crosslinking group site is unchanged compared to the fluorinated resin precursor 6 used (same as before the introduction of the crosslinking group).

[0201] Synthesis of Fluorine-Containing Resin 7 10 g of fluorinated resin precursor 7 (with an alcoholic hydroxyl equivalent of 0.018 mol) and 20 g of PGMEA were weighed into a 300 ml glass flask equipped with a stirrer, and 2.52 g (0.018 mol) of Karenz-AOI was added. The mixture was reacted at 45 °C for 5 hours. After the reaction was completed, the reaction solution was concentrated, and 150 g of n-heptane was added to precipitate the precipitate. The precipitate was filtered and dried under reduced pressure at 40 °C to obtain 12.0 g of fluorinated resin 7 as a white solid in a yield of 96%.

[0202] < 13 C-NMR measurement results > In fluorinated resin 7, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual alcoholic hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from AN, monomer unit from MA-C4F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 7 used (same as before the introduction of the crosslinking group).

[0203] Synthesis of Fluorine-Containing Resin 8 Except that fluorinated resin precursor 8 is used instead of fluorinated resin precursor 7, fluorinated resin 8 is obtained in 93% yield by the same steps as the synthesis of fluorinated resin 7.

[0204] < 13 C-NMR measurement results > In fluorinated resin 8, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual alcoholic hydroxyl groups (unreacted rate) were expressed in a molar ratio of 97:3. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MN, monomer unit from MA-C6F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 8 used (same as before the introduction of the crosslinking group).

[0205] Synthesis of Fluorine-Containing Resin 9 Except that fluorinated resin precursor 9 is used instead of fluorinated resin precursor 7, fluorinated resin 9 is obtained in 90% yield by the same steps as the synthesis of fluorinated resin 7.

[0206] < 13 C-NMR measurement results > In fluorinated resin 9, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 95:5. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from AN, monomer unit from MA-C6F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 9 used (same as before the introduction of the crosslinking group).

[0207] Synthesis of Fluorine Resin 10 Except that fluorinated resin precursor 10 is used instead of fluorinated resin precursor 7, fluorinated resin 10 is obtained in 93% yield by the same steps as the synthesis of fluorinated resin 7.

[0208] < 13 C-NMR measurement results > In the fluorinated resin 10, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MN, monomer unit from MA-C4F) that did not react with the crosslinking group site remained unchanged compared to the fluorinated resin precursor 10 used (same as before the introduction of the crosslinking group).

[0209] [Comparison of the synthesis of fluorinated resin 1] Except that comparative fluorinated resin precursor 1 was used instead of fluorinated resin precursor 1, comparative fluorinated resin 1 was obtained in 89% yield by the same steps as the synthesis of fluorinated resin 1.

[0210] < 13 C-NMR measurement results > In comparative fluorinated resin 1, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MA-C6F and monomer unit from HFIP-M) that did not react with the crosslinking group sites remained unchanged compared to comparative fluorinated resin precursor 1 (same as before the introduction of the crosslinking group).

[0211] [Comparison of the synthesis of fluorinated resin 2] Except that comparative fluorinated resin precursor 2 is used instead of fluorinated resin precursor 1, comparative fluorinated resin 2 is obtained in 90% yield by the same steps as the synthesis of fluorinated resin 1.

[0212] < 13 C-NMR measurement results > In comparative fluorinated resin 2, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 96:4. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MA-C6F and monomer unit from HFIP-M) that did not react with the crosslinking group sites remained unchanged compared to comparative fluorinated resin precursor 2 (same as before the introduction of the crosslinking group).

[0213] [Comparison of the synthesis of fluorinated resin 3] Except that comparative fluorinated resin precursor 3 is used instead of fluorinated resin precursor 1, comparative fluorinated resin 3 is obtained in 90% yield by the same steps as the synthesis of fluorinated resin 1.

[0214] < 13 C-NMR measurement results > In comparative fluorinated resin 3, the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were expressed in a molar ratio of 95:5. Furthermore, it was confirmed that the composition ratio of each repeating unit (monomer unit from MA-C6F) that did not react with the crosslinking group site remained unchanged compared to the comparative fluorinated resin precursor 3 used (same as before the introduction of the crosslinking group).

[0215] 4. Preparation of photosensitive resin composition [Preparation of Photosensitive Resin Composition 1] A photosensitive resin composition 1 was prepared by filtering a solution obtained by blending 0.5 parts by weight of the prepared fluorinated resin 1, 0.5 parts by weight of Irgacure 369 (a product of BASF Corporation) as a photopolymerization initiator, 50 parts by weight of pentaerythritol tetraacrylate (a product of TOKYO CHEMICAL INDUSTRY CO.,LTD.) as a crosslinking agent, 50 parts by weight of ZAR2051H (a product of Nippon Kayaku Co.,Ltd.) as an alkali-soluble resin, 160 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and 70 parts by weight of propylene glycol monomethyl ether (PGME) as solvents using a 0.2 μm membrane filter.

[0216] [Preparation of Photosensitive Resin Composition 2] Except that fluorinated resin 2 is used instead of fluorinated resin 1, photosensitive resin composition 2 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0217] [Preparation of Photosensitive Resin Composition 3] Except that fluorinated resin 3 is used instead of fluorinated resin 1, photosensitive resin composition 3 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0218] [Preparation of Photosensitive Resin Composition 4] Except that fluorinated resin 4 is used instead of fluorinated resin 1, photosensitive resin composition 4 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0219] [Preparation of photosensitive resin composition 5] Except that fluorinated resin 5 is used instead of fluorinated resin 1, photosensitive resin composition 5 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0220] [Preparation of Photosensitive Resin Composition 6] Except that fluorinated resin 6 is used instead of fluorinated resin 1, photosensitive resin composition 6 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0221] [Preparation of photosensitive resin composition 7] Except that fluorinated resin 7 is used instead of fluorinated resin 1, photosensitive resin composition 7 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0222] [Preparation of photosensitive resin composition 8] Except that fluorinated resin 8 is used instead of fluorinated resin 1, photosensitive resin composition 8 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0223] [Preparation of photosensitive resin composition 9] Except that fluorinated resin 9 is used instead of fluorinated resin 1, photosensitive resin composition 9 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0224] [Preparation of photosensitive resin composition 10] Except that fluorinated resin 10 is used instead of fluorinated resin 1, photosensitive resin composition 10 is prepared using the same steps as the preparation of photosensitive resin composition 1.

[0225] [Preparation of Comparative Photosensitive Resin Composition 1] The comparative photosensitive resin composition 1 was prepared using the same steps as the preparation of the photosensitive resin composition 1, except that the comparative fluorinated resin 1 was used instead of the fluorinated resin 1.

[0226] [Preparation of Comparative Photosensitive Resin Composition 2] The comparative photosensitive resin composition 2 was prepared using the same steps as the preparation of the photosensitive resin composition 1, except that the comparative fluorinated resin 2 was used instead of the fluorinated resin 1.

[0227] [Preparation of Comparative Photosensitive Resin Composition 3] The comparative photosensitive resin composition 3 was prepared using the same steps as the preparation of the photosensitive resin composition 1, except that the comparative fluorinated resin 3 was used instead of the fluorinated resin 1.

[0228] 5. Evaluation of the dike Using the photosensitive resin compositions 1-10 obtained in "4. Preparation of Photosensitive Resin Compositions" and comparative photosensitive resin compositions 1-3, barrier 1-10 and comparative barrier 1-3 were formed, and the barrier performance was evaluated and compared. The results of the barrier of the present invention and the results of the comparative barrier are shown in Table 1.

[0229] [The formation of the dike] A 10cm square ITO substrate was cleaned with ultrapure water and then with acetone. The substrate was then subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by SENLIGHT SCo., Ltd., model: PL17-110). Next, photosensitive resin compositions 1-10 and comparative photosensitive resin compositions 1-3 obtained in "4. Preparation of Photosensitive Resin Compositions" were coated onto the UV-ozone-treated substrate using a spin coater at a speed of 1,000 rpm. The substrate was then heated at 100°C for 150 seconds on a heated plate to form a 2μm thick fluorinated resin film and a comparative fluorinated resin film. Using a mask aligner (a product of SUSS MicroTec K.K.), the obtained resin film was exposed to i-lines (wavelength 365nm) through a mask with a linewidth / pitch of 5μm. The obtained exposed resin film was evaluated for its solubility in the developer, its barrier properties (sensitivity, resolution), and its contact angle was measured.

[0230] [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 separator was evaluated by measuring the film thickness of the impregnated separator using a contact film thickness gauge. Complete dissolution of the separator was recorded as "soluble," and the absence of dissolved separator residue was recorded as "insoluble." The results are shown in Table 1.

[0231] [Dike performance (sensitivity, resolution)] Determine the optimal exposure Eop (mJ / cm) for forming the above line width / spacing pattern, i.e., for forming the dike. 2 ), and use it as an indicator of sensitivity. Furthermore, the resolution was evaluated by observing the obtained dike patterns under a microscope. Patterns where line edge roughness could not be identified were categorized as "Excellent," those where line edge roughness was slightly identified as "Good," and those with significant line edge roughness as "Unacceptable." The results are shown in Table 1.

[0232]

[0233] [Contact Angle] After heating the substrate with partitions obtained through the above process to 230°C for 60 minutes, the entire surface of the substrate was subjected to UV ozone treatment or oxygen plasma treatment for 10 minutes. Then, it was heated to 230°C for 60 seconds. Before and after the UV ozone treatment or oxygen plasma treatment, and after the subsequent heating process, the contact angles of each partition surface with anisole, PGMEA, and water were measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: DMs-601). The results are shown in Table 2. In addition, the UV ozone treatment device used is the same as the UV ozone treatment device mentioned above. In addition, as an oxygen plasma treatment device, a plasma cleaner PDC210 manufactured by Yamato Scientific Co., Ltd. was used to perform oxygen plasma treatment under conditions of oxygen flow rate of 30cc / min and power of 300W.

[0234]

[0235] As shown in Table 1, both the barrier of the present invention and the comparative barrier are negative resists that only failed to dissolve in the exposed portion during the evaluation of developer solubility. They exhibited the same level of sensitivity in the barrier performance evaluation, transferring a 5μm linewidth / spacing of the mask with good resolution. No line edge roughness was observed, and both achieved "Excellent" resolution. Therefore, based on these evaluations, it can be concluded that the fluorinated resin of the present invention and the comparative fluorinated resin have a relatively small impact on the barrier.

[0236] On the other hand, as shown in Table 2, in the barrier of the present invention, although the contact angle of the exposed portion (corresponding to the upper surface of the barrier) to anisole, PGMEA, and water is reduced due to UV ozone treatment or oxygen plasma treatment, it increases through the subsequent heating process, exhibiting good liquid repellency. In the comparative barrier, the contact angle is reduced due to UV ozone treatment or oxygen plasma treatment, and even through the subsequent heating process, the contact angle remains low with almost no change.

Claims

1. The use of a fluorinated resin in the fabrication of partition walls that divide areas into which a light-emitting layer is disposed, characterized in that, The fluorinated resin contains repeating units (U), which are comprised of monomers (A) having triple bonds in their side chains and monomers (B) having the structure represented by formula (4) or formula (4') as monomer units. CH2=C(R 1 )COOR f …(4) CH2=C(R 1 )COOXR f …(4’) In equations (4) and (4'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a straight-chain 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 straight-chain alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms may optionally be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to straight-chain perfluoroalkyl groups with 1 to 6 carbon atoms, branched perfluoroalkyl groups with 3 to 6 carbon atoms, or cyclic perfluoroalkyl groups with 3 to 6 carbon atoms.

2. The application according to claim 1, wherein, The fluorine-containing resin contains fluorine atoms at a content of 5% by mass or more.

3. The application according to claim 1 or 2, wherein, At least a portion of the side chain of the monomer (A) contains fluorine atoms.

4. The application according to claim 1 or 2, wherein, At least a portion of the triple bond is a carbon-nitrogen triple bond of a cyano group.

5. The application according to claim 1 or 2, wherein, At least a portion of the monomer (A) has the structure represented by formula (1) or formula (1'): CH2=C(R 1 )C≡CR 2 …(1) CH2=C(R 1 )XC≡CR 2 …(1’) In equations (1) and (1'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a straight-chain 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 straight-chain alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms may optionally be substituted with a hydroxyl group or -OC(=O)-CH3; R 2 The term refers to a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the straight-chain alkyl group having 1 to 15 carbon atoms, the branched alkyl group having 3 to 15 carbon atoms, or the cyclic alkyl group having 3 to 15 carbon atoms may optionally be replaced by fluorine atoms.

6. The application according to claim 5, wherein, The structure represented by equation (1) or (1') is the same as the structure represented by equation (2) or (2') below: CH2=C(R 1 )C≡CR f …(2) CH2=C(R 1 )XC≡CR f …(2’) In equations (2) and (2'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a straight-chain 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 straight-chain alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms may optionally be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to straight-chain perfluoroalkyl groups with 1 to 6 carbon atoms, branched perfluoroalkyl groups with 3 to 6 carbon atoms, or cyclic perfluoroalkyl groups with 3 to 6 carbon atoms.

7. The application according to claim 1 or 2, wherein, At least a portion of the monomer (A) is acrylonitrile and / or methacrylonitrile.

8. The use of a photosensitive resin composition in the fabrication of a partition wall that divides the area where a light-emitting layer is disposed, characterized in that, The photosensitive resin composition comprises at least: a fluorinated resin, a solvent, and a photopolymerization initiator. The fluorinated resin contains repeating units (U), which are comprised of monomers (A) having triple bonds in their side chains and monomers (B) having the structure represented by formula (4) or formula (4') as monomer units. CH2=C(R 1 )COOR f …(4) CH2=C(R 1 )COOXR f …(4’) In equations (4) and (4'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a straight-chain 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 straight-chain alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms may optionally be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to straight-chain perfluoroalkyl groups with 1 to 6 carbon atoms, branched perfluoroalkyl groups with 3 to 6 carbon atoms, or cyclic perfluoroalkyl groups with 3 to 6 carbon atoms.

9. The application according to claim 8, wherein the photosensitive resin composition further comprises a crosslinking agent and an alkali-soluble resin.

10. The application according to claim 8 or 9, wherein, The solvent comprises at least one selected from the group consisting of ketones, alcohols, ethers, esters, aromatic solvents, and fluorinated solvents.

11. The application according to claim 8 or 9, wherein, The solvent includes polyols and their derivatives.

12. The application according to claim 8 or 9, wherein, The photopolymerization initiator includes a photoradical initiator and / or a photoacid initiator.

13. A partition wall for dividing a region into which a light-emitting layer is disposed, characterized in that, It is formed by curing a photosensitive resin composition. The photosensitive resin composition comprises at least: a fluorinated resin, a solvent, and a photopolymerization initiator. The fluorinated resin contains repeating units (U), which are comprised of monomers (A) having triple bonds in their side chains and monomers (B) having the structure represented by formula (4) or formula (4') as monomer units. CH2=C(R 1 )COOR f …(4) CH2=C(R 1 )COOXR f …(4’) In equations (4) and (4'), R 1 Represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a straight-chain 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 straight-chain alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms may optionally be substituted with a hydroxyl group or -OC(=O)-CH3; R f It refers to straight-chain perfluoroalkyl groups with 1 to 6 carbon atoms, branched perfluoroalkyl groups with 3 to 6 carbon atoms, or cyclic perfluoroalkyl groups with 3 to 6 carbon atoms.

14. A display, characterized in that, It includes a light-emitting element, the light-emitting element comprising: a partition wall dividing a region in which a light-emitting layer is disposed as described in claim 13; and a light-emitting layer disposed in the region divided by the partition wall.

15. The display according to claim 14, wherein it is an organic EL display or a quantum dot display.

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