TWI895532B - Fluorine-containing resin, repellent, photosensitive resin composition, cured product, and display - Google Patents

Abstract

The present invention provides a fluorinated resin capable of forming barrier ribs (partition walls) whose repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment. The fluorinated resin of the present invention is characterized by comprising a repetitive unit (U) comprising a monomer (A) having a triple-bonded side chain as a monomer unit.

Description

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

The present invention relates to a fluorine-containing resin, a repellent, a photosensitive resin composition, a cured product, and a display.

Inkjet printing is a well-known method for forming organic layers with luminescent properties when manufacturing display devices such as organic EL (electroluminescence) displays, micro-LED (light-emitting diode) displays, and quantum dot displays. Several inkjet methods exist, including: one in which ink dripped from a nozzle onto the concave portions of a patterned film with reliefs formed on a substrate is cured; another in which ink is dropped onto a patterned film pre-formed on the substrate, forming a lyophilic portion (wetted by the ink) and a lyophilic portion (unwetted by the ink), and then depositing ink drops onto the patterned film, ensuring that the ink adheres only to the lyophilic portion.

In particular, in the method cited above of solidifying the ink dripped from the nozzle to the concave portion of the pattern film, there are two main methods that can be used to produce such a pattern film with concave and convex surfaces. One is the photolithography method, which forms exposed and unexposed portions by exposing the surface of the photosensitive anti-etching film coated on the substrate in a patterned manner, and dissolving and removing any portion with a developer; the other is the embossing method using printing technology. Usually, after the pattern film with concave and convex surfaces is formed, the entire surface of the substrate is subjected to UV (ultraviolet) ozone treatment or oxygen plasma treatment. By means of the UV ozone treatment or oxygen plasma treatment, residual organic matter in the concave portion of the pattern film can be removed, and uneven wetting of the dripped ink can be reduced, thereby preventing malfunctions of the display element before they occur.

The raised areas of the resulting concave-convex pattern film are called barriers (partition walls). When ink is dripped into the concave areas of the pattern film, the barriers act as a barrier, preventing the ink from mixing. To enhance this barrier effect, the substrate surface exposed in the concave areas of the pattern film must be lyophilic to the ink, and the upper surface of the barrier must be repellent to the ink.

Fluorine-containing resins can be used as the resin for forming such a barrier. Fluorine-containing resins improve liquid repellency.

Patent document 1 discloses an anti-corrosion agent composition containing a fluorine-containing resin, wherein the anti-corrosion agent composition comprises a fluorine-containing resin (A) having a monomer unit formed by a monomer represented by Formula 1 and a fluorine atom content of 7 to 35 mass %, and a fluorine-containing resin (A) having ... The photosensitive component that reacts to light of 100 nm is prepared by mixing the fluorinated resin (A) in an amount of 0.1 to 30% by mass relative to the total solid content of the anti-corrosion composition. The photosensitive component comprises: a photoacid generator (B); an alkali-soluble resin (C) having carboxyl groups and/or phenolic hydroxyl groups; and an acid crosslinking agent (D) having two or more groups capable of reacting with carboxyl groups or phenolic hydroxyl groups by the action of an acid. CH ₂ =C(R ¹ )COOXR ^f ･･･Formula 1 In Formula 1, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, X represents a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms.

Patent Document 2 discloses an ink repellent containing fluorine-containing polymeric units. The ink repellent comprises a polymer having polymeric units (b1) and polymeric units (b2), wherein the polymeric units (b1) have an alkyl group having 20 or fewer carbon atoms (including an ethereal oxygen group) in which at least one hydrogen atom is substituted with a fluorine atom, and the polymeric units (b2) have an ethylenic double bond. 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.

Patent Document 3 discloses an anti-etching composition containing a fluorinated resin. The anti-etching composition comprises a fluorinated resin (A) having monomer units formed from a monomer represented by Formula 1, having ethylenic double bonds, and a fluorine atom content of 7 to 35% by mass; and a photosensitive component that reacts to light having a wavelength of 100 to 600 nm. The ratio of the fluorinated resin (A) is 0.1 to 30% by mass relative to the total solid content of the anti-etching composition. The photosensitive component comprises a photoradical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds per molecule. CH ₂ =C(R ¹ )COOXR ^f ･･･Formula 1 In Formula 1, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, X represents a divalent organic group having 1 to 6 carbon atoms and not containing a fluorine atom, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms.

Patent Document 4 discloses a negative photosensitive resin composition containing an ink repellent having fluorine atoms. The composition comprises 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 content of the fluorine atoms in the ink repellent (E) is 1 to 40% by mass, and the ink repellent (E) has an ethylenic double bond.

Patent Document 5 discloses a photosensitive resin composition having excellent repellency, 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 containing a hydrocarbon having a fluorine atom. Prior Art Documents Patent Documents

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

[Identify the problem you want to solve]

When using the anti-etching compositions described in Patent Documents 1 to 4 to form barrier ribs (partition walls), the cured resin has excellent liquid repellency, but suffers from a problem in that the liquid repellency decreases when subjected to the aforementioned UV ozone treatment or oxygen plasma treatment.

The present invention is to provide a fluorinated resin that can be used to produce barrier ribs (partition walls) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment. [Technical Solution]

In light of the above-mentioned problems, the inventors conducted intensive research and discovered that the above-mentioned problems can be solved by using a monomer with a triple-bond side chain, thus completing the present invention.

By using the fluorine-containing resin of the present invention, it is possible to produce barrier ribs (partition ribs) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment.

That is, the present invention is as follows.

The fluorine-containing resin of the present invention is characterized in that it contains a monomer (A) having a triple bond in the side chain as a repetitive unit (U).

The fluorine-containing resin of the present invention preferably has a fluorine atom content of 5% by mass or more.

The fluorine-containing resin of the present invention preferably contains fluorine atoms in at least a portion of the side chains of the monomer (A).

In the fluorine-containing resin of the present invention, a carbon-nitrogen triple bond in which at least a portion of the triple bond is a nitrile group is preferred.

In the fluorinated resin of the present invention, it is preferred that at least a portion of the monomer (A) has a structure represented by the following formula (1) or formula (1'). CH ₂ =C(R ¹ )C≡CR ² ･･･(1) CH ₂ =C(R ¹ )XC≡CR ² ･･･(1´) (In formulas (1) and (1´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxy group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, 3 to 15 carbon atoms, or 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a fluorine atom)

In the fluorinated resin of the present invention, the structure represented by the above formula (1) or (1') is preferably a structure represented by the following formula (2) or (2'). CH ₂ =C(R ¹ )C≡CR ^f ･･･(2) CH ₂ =C(R ¹ )XC≡CR ^f ･･･(2´) (In formulas (2) and (2´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms; any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH ₃ ; R ^f represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms)

The fluorinated resin of the present invention preferably comprises the above-mentioned repeating unit (U) comprising the above-mentioned monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3') as monomer units. CH ₂ =C(R ¹ )COOR ² ･･･(3) CH ₂ =C(R ¹ )COOXR ² ･･･(3´) (In formulas (3) and (3´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxy group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, 3 to 15 carbon atoms, or 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a fluorine atom)

The fluorinated resin of the present invention preferably has a structure represented by the above formula (3) or formula (3') or a structure represented by the following formula (4) or formula (4'). CH ₂ =C(R ¹ )COOR ^f ･･･(4) CH ₂ =C(R ¹ )COOXR ^f ･･･(4´) (In formulas (4) and (4´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms; any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH ₃ ; R ^f represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms)

The repellent of the present invention is characterized by comprising the above-mentioned fluorine-containing resin of the present invention.

The photosensitive resin composition of the present invention is characterized by comprising at least the fluorine-containing resin of the present invention, a solvent, and a photopolymerization initiator.

The photosensitive resin composition of the present invention preferably further comprises a crosslinking agent and an alkaline-soluble resin.

The photosensitive resin composition of the present invention is preferably used for forming partition walls.

The characteristic of the cured product of the present invention is that it is formed by curing the above-mentioned photosensitive resin composition of the present invention.

The display of the present invention is characterized by including a light-emitting element having: Partition walls comprising the cured article of the present invention; and A light-emitting layer disposed in the region defined by the partition walls.

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

According to the present invention, it is possible to produce a barrier rib (partition rib) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment.

The present invention is described in detail below. The description of the constituent elements described below is an example of an embodiment of the present invention. The present invention is not limited to the specific contents and can be implemented in various modifications within the scope of the present invention.

In the "Embodiments" section of this specification, the terms "[" and "]", "<" and ">" are merely symbols and have no inherent meaning. In this specification, "polymer" and "resin" are synonymous and, unless otherwise noted, refer to high molecular weight compounds.

In this specification, "barrier" and "spacer" are synonymous and, unless otherwise noted, refer to the convex portion of a patterned film having concave and convex surfaces in an inkjet process.

(Fluoro-Resin) The fluorine-containing resin of the present invention is characterized by comprising a monomer (A) having a triple-bonded side chain as a repetitive unit (U).

By using the fluorinated resin of the present invention, barrier ribs (partition ribs) with sufficiently high liquid repellency can be produced. Furthermore, even after UV ozone treatment or oxygen plasma treatment, the resulting barrier ribs (partition ribs) exhibit a low level of liquid repellency. The reason for producing such highly liquid repellent barrier ribs (partition ribs) is speculated to be as follows. First, it is believed that surface segregation of fluoroalkyl groups enhances liquid repellency. As described below, when using the fluorinated resin of the present invention to produce barrier ribs (partition ribs), UV ozone treatment or oxygen plasma treatment is performed after forming a patterned film, 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 allows the π electrons of the triple bonds to interact with the -CH, -OH, and -NH bonds, immobilizing these functional groups. On the other hand, fluorinated alkyl groups, which interact less strongly with the π electrons of the triple bonds, tend to segregate on the surface. Subsequent heating promotes rearrangement, improving liquid repellency.

In this specification, "a monomer (A) having a triple bond in a side chain" refers to a monomer having a triple bond at a position that becomes a side chain in a polymer formed from monomer (A). In this specification, "a repeating unit (U)" refers to a monomer unit that constitutes the main chain of a fluororesin and refers to a plurality of monomer units present in that main chain. Furthermore, the repeating units (U) may constitute the main chain of the fluororesin continuously, or other monomer units may be present between the repeating units (U). Furthermore, monomer units other than the repeating units (U) may be present at the ends of the main chain of the fluororesin.

The fluorine-containing resin of the present invention preferably has a fluorine atom content of 5% by mass or greater. Also, the fluorine atom content is preferably 50% by mass or less. A fluorine atom content of 5% by mass or greater can produce a barrier with even higher liquid repellency.

Furthermore, in this specification, the "fluorine atom content of a fluorinated resin" refers to a value calculated based on the molar ratio of 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). Herein, a method for determining the fluorine content in a fluorinated resin obtained by polymerizing 1,1-bis(trifluoromethyl)butadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate is described. (i) First, the ratio (molar ratio) of each component is calculated by NMR measurement of the fluorinated resin. (ii) Multiply the molecular weight (Mw) of the monomers in each component of the fluorinated resin by the molar ratio, add the obtained values, and calculate the total. Calculate the weight ratio (wt%) of each component from this total. Furthermore, the molecular weight of 1,1-bis(trifluoromethyl)butadiene is 190, the molecular weight of 1,1-bis(trifluoromethyl)butadiene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432. (iii) Next, calculate the fluorine content of the monomers in the fluorine-containing components. (iv) Calculate the "fluorine content of the monomers" for each component by dividing the monomer molecular weight (Mw) by the weight ratio (wt%) and sum the obtained values. (v) Calculate the "value obtained in (iv) above" / "the total value obtained in (ii) above" to calculate the fluorine atom content of the fluorine-containing resin.

In the fluorinated resin of the present invention, it is preferred that at least a portion of the monomer (A) has a structure represented by the following formula (1) or formula (1'). CH ₂ =C(R ¹ )C≡CR ² ･･･(1) CH ₂ =C(R ¹ )XC≡CR ² ･･･(1´) (In formulas (1) and (1´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxy group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, 3 to 15 carbon atoms, or 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a fluorine atom)

Furthermore, in the fluorine-containing resin of the present invention, it is preferred that the structure represented by the above formula (1) or (1') is a structure represented by the following formula (2) or (2'). CH ₂ =C(R ¹ )C≡CR ^f ･･･(2) CH ₂ =C(R ¹ )XC≡CR ^f ･･･(2´) (In formulas (2) and (2´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms; any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH ₃ ; R ^f represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms)

As preferred structures of Formula (1) and Formula (1') (including preferred structures of Formula (2) and Formula (2')), the structures represented by the following Formulas (1-1) to (1-4) and (2-1) to (2-4) can be cited.

CH ₂ =CHC≡CCF ₂ H･･･(1-1) CH ₂ =CHC≡CC ₂ F ₄ H･･･(1-2) CH ₂ =C(CH ₃ )C≡CCF ₂ H･･･(1-3) CH ₂ =C(CH ₃ )C≡CC ₂ F ₄ H･･･(1-4) CH ₂ =CHC≡CCF ₃ ･･･(2-1) CH ₂ =CHC≡CC ₄ F ₉ ･･･(2-2) CH ₂ =C(CH ₃ )C≡CCF ₃ ･･･(2-3) CH ₂ =C(CH ₃ )C≡CC ₄ F ₉ ･･･(2-4)

Furthermore, in the fluorinated resin of the present invention, it is preferred that the repeating unit (U) comprises the above-mentioned monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3') as monomer units.

CH ₂ =C(R ¹ )COOR ² ･･･(3) CH ₂ =C(R ¹ )COOXR ² ･･･(3´) (In formulas (3) and (3´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxy group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, 3 to 15 carbon atoms, or 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a fluorine atom)

Furthermore, the monomers represented by formula (3) and formula (3') preferably have structures represented by the following formula (4) and formula (4').

CH ₂ =C(R ¹ )COOR ^f ･･･(4) CH ₂ =C(R ¹ )COOXR ^f ･･･(4´) (In formulas (4) and (4´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms; any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH ₃ ; R ^f represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms)

Regarding Formula (4) and Formula (4'), the following structures of Formula (4'-1) to (4'-3) can be cited as more preferable structures.

CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₆ F ₁₃ ･･･(4´-1) CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₄ F ₉ ･･･(4´-2) CH ₂ =C(CH ₃ )COOCH(CF ₃ )CF ₃ ･･･(4´-3)

When the repeating unit (U) of the fluorinated resin of the present invention includes two or more structures of different types among the structures represented by formula (1), formula (1'), formula (2), formula (2'), formula (3), formula (3'), formula (4), and formula (4'), R ¹ , R ² , R ^f , and X in each structure may be the same or different.

The fluorine-containing resin of the present invention preferably contains fluorine atoms in the side chains of at least a portion of the monomer (A). Furthermore, the fluorine atoms may be positioned at positions forming side chains in the structures represented by Formula (1), Formula (1'), Formula (2), or Formula (2'), or may be positioned at positions forming side chains in other structures.

In the fluorinated resin of the present invention, a carbon-nitrogen triple bond in which at least a portion of the triple bond is a nitrile group is preferred. Fluorine atoms may be positioned as side chains in the structures represented by formula (1), formula (1'), formula (2), or formula (2'), or may be positioned as side chains in other structures.

The molecular weight of the fluororesin of the present invention, as measured by gel permeation chromatography (GPC) using polystyrene as a standard, is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and even more preferably 3,000 to 100,000. If the molecular weight is less than 1,000, the strength of the resulting fluororesin film or barrier rib for organic EL tends to decrease. If the molecular weight is greater than 1,000,000, the solubility in solvents is insufficient, making it difficult to form a fluororesin film by coating.

The dispersion index (Mw/Mn) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and even more preferably 1.01 to 3.00.

The fluorine-containing resin of the present invention can be used in repellents or photosensitive resin compositions.

(Photosensitive Resin Composition) The photosensitive resin composition of the present invention is characterized by comprising at least the fluorinated resin of the present invention, a solvent, and a photopolymerization initiator.

The photosensitive resin composition of the present invention can be used to form barrier ribs (partition walls). Because it contains the fluorinated resin of the present invention, barrier ribs (partition walls) with sufficiently high liquid repellency can be produced. Furthermore, even after UV ozone treatment or oxygen plasma treatment, the liquid repellency of the produced barrier ribs (partition walls) is not easily reduced.

The solvent contained in the photosensitive resin composition of the present invention is not particularly limited as long as the fluorinated resin is soluble therein. Examples include ketones, alcohols, polyols and their derivatives, ethers, esters, aromatic solvents, and fluorinated solvents. These solvents may be used alone or in combination of two or more.

Specific examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isoamyl ketone, and 2-heptanone. Specific examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

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

Specific examples of the ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

Specific examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone. Examples of aromatic solvents include xylene and toluene.

Examples of fluorine-based solvents include fluorochlorocarbons, hydrofluorochlorocarbons, perfluoro compounds, and hexafluoroisopropyl alcohol.

In order to improve the coating properties, a turpentine-based naphtha solvent or a wax-based solvent, which is a high-boiling-point weak solvent, can be used.

Among them, the solvent is preferably at least one selected from the group consisting of methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate 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 at least one selected from 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.

The amount of solvent in the photosensitive resin composition of the present invention is preferably within a range of 50 to 2,000 parts by mass relative to 100 parts by mass of the fluorinated resin concentration (wherein, when the photosensitive resin composition includes an alkali-soluble resin, this is the total concentration including the alkali-soluble resin described below). More preferably, it is 100 to 1,000 parts by mass. Adjusting the amount of solvent can adjust the thickness of the resulting resin film. When the amount of solvent is within this range, a resin film thickness particularly suitable for forming barrier ribs for organic EL can be achieved.

The photopolymerization initiator contained in the photosensitive resin composition of the present invention is not particularly limited, as long as it polymerizes monomers having polymerizable double bonds by high-energy radiation such as electromagnetic waves or electron beams. Known photopolymerization initiators can be used. Photopolymerization initiators can be photoradical initiators or photoacid initiators. These can be used alone or in combination, or two or more photoradical initiators or photoacid initiators can be mixed. Furthermore, by using an additive simultaneously with the photopolymerization initiator, living polymerization can be achieved, if appropriate. Such additives can be known additives.

Photoradical initiators can be specifically categorized into two types: intramolecular bond-breaking type, in which bonds within a molecule are broken by absorption of electromagnetic waves or electron beams, generating free radicals; and hydrogen-absorptive type, in which free radicals are generated by combining with hydrogen donors such as tertiary amines or ethers. All of these types can be used. Photoradical initiators other than the types listed above can also be used.

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

Specific 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 them, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

Specific examples of acetophenone-based compounds include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-oxolinyl-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-oxolinylphenyl)-butan-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

Specific examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylcarboxylate, and 9,10-phenanthrenequinone. Among them, 4,4'-dimethoxybenzyl and methyl benzoylcarboxylate are preferred.

Specific examples of the acylphosphine oxide series include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and the like.

Specific examples of the quinone-based compounds include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among them, camphorquinone and 1,4-naphthoquinone are preferred.

Specific examples of the alcohol ketone series include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among them, benzoin and benzoin methyl ether are preferred.

As the photoradical initiator, benzophenone-based, acetophenone-based, and diketone-based are preferred, and benzophenone-based are more preferred.

Among commercially available photoradical initiators, preferred examples include Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, and Lucirin TPO, all manufactured by BASF. Among these, Irgacure 651 and Irgacure 369 are more preferred.

The photoacid initiator specifically comprises a photoacid selected from aromatic sulfonic acid, aromatic iodine, aromatic diazonium, aromatic ammonium, thianthrenium, 9-oxosulfuronium, An onium salt of at least one cation selected from the group consisting of bis(2,4-cyclopentadien-1-yl)(1-methylethylphenyl)iron, and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. Among them, bis[4-(diphenylsectonyl)phenyl]sulfide bis(hexafluorophosphate), bis[4-(diphenylsectonyl)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

Examples of commercially available photoacid initiators include: CPI-100P, CPI-110P, CPI-101A, CPI-200K, and CPI-210S manufactured by San-Apro Co., Ltd.; Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, and Cyracure Photocuring Initiator UVI-6976 manufactured by Dow Chemical Japan Co., Ltd.; and Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, and Adeka Optomer SP-176 manufactured by Adeka Co., Ltd. SP-300; CI-5102 and CI-2855 manufactured by Nippon Soda Co., Ltd.; San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110 and San-Aid SI-180 manufactured by San Hsin Chemical Industry Co., Ltd.; Esacure 1064 and Esacure 1187 manufactured by Lamberti; Irgacure 250 manufactured by BASF GmbH.

The content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass, and more preferably from 1 to 20 parts by mass, relative to 100 parts by mass of the fluorinated resin (wherein, when the photosensitive resin composition includes an alkali-soluble resin described below, this is the total concentration including such resin). If the content of the photopolymerization initiator is less than 0.1 parts by mass, the crosslinking effect tends to be insufficient, while if it exceeds 30 parts by mass, the resolution or sensitivity tends to decrease.

The photosensitive resin composition of the present invention may contain, in addition to the essential components of the fluorinated resin, solvent, and photopolymerization initiator, a crosslinking agent, an alkali-soluble resin, a naphthoquinone diazide-containing compound, an alkaline compound, and other additives.

The crosslinking agent contained in the photosensitive resin composition of the present invention reacts with the repeating units (U) of the fluorinated resin to form a crosslinked structure in the resin, thereby improving the mechanical strength of the formed film.

Crosslinking agents that can be used are known. Specific examples include compounds formed by reacting formaldehyde or formaldehyde and a lower alcohol with an amino-containing compound such as melamine, ethylguanidine, benzoguanamine, urea, ethylurea, propylurea, or glycoluril, where the hydrogen atoms of the amino groups are replaced with hydroxymethyl or lower alkoxymethyl groups; polyfunctional epoxy compounds, polyfunctional oxycyclobutane compounds, polyfunctional isocyanate compounds, and polyfunctional acrylate compounds. Herein, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using urea is referred to as a urea-based crosslinking agent, a crosslinking agent using an alkylurea such as ethylurea or propylurea is referred to as an alkylurea-based crosslinking agent, and a crosslinking agent using glycoluril is referred to as a glycoluril-based crosslinking agent. These crosslinking agents may be used alone or in combination of two or more.

The crosslinking agent is preferably at least one selected from the above crosslinking agents, and more preferably a glycoluril crosslinking agent or a multifunctional acrylate compound.

Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine. Among them, hexamethoxymethylmelamine is preferred.

Examples of urea-based crosslinking agents include bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea. Among them, bismethoxymethyl urea is preferred.

Examples of the alkylene urea crosslinking agent include ethylurea crosslinking agents such as mono- and/or dihydroxymethylated ethylurea, mono- and/or dimethoxymethylated ethylurea, mono- and/or diethoxymethylated ethylurea, mono- and/or dipropoxymethylated ethylurea, and mono- and/or dibutoxymethylated ethylurea; propylurea crosslinking agents such as mono- and/or dihydroxymethylated propylurea, mono- and/or dimethoxymethylated propylurea, mono- and/or diethoxymethylated propylurea, mono- and/or dipropoxymethylated propylurea, and mono- and/or dibutoxymethylated propylurea; and 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

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

Examples of the multifunctional acrylate compound include multifunctional acrylates (e.g., products manufactured by Shin-Nakamura Chemical Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and AD-TMP), polyethylene glycol diacrylates (e.g., products manufactured by Shin-Nakamura Chemical Co., Ltd.: A-200, A-400, and 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, and UA-7200), and pentaerythritol tetraacrylate.

Preferred polyfunctional acrylate compounds are exemplified below.

[Chemistry 1]

[Chemistry 2]

[Chemistry 3]

The content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 10 to 300 parts by mass, and more preferably 50 to 200 parts by mass, relative to 100 parts by mass of the fluorinated resin (wherein, when the photosensitive resin composition includes an alkali-soluble resin, as described below), and is more preferably 10 to 300 parts by mass. If the crosslinking agent content is less than 10 parts by mass, the crosslinking effect tends to be insufficient, while if it exceeds 300 parts by mass, resolution or sensitivity tends to decrease.

If the photosensitive resin composition of the present invention contains an alkali-soluble resin, the shape of the barrier ribs obtained from the photosensitive resin composition of the present invention can be improved.

Examples of alkali-soluble resins include alkali-soluble novolac resins. Alkali-soluble novolac resins can be obtained by condensing phenols with aldehydes in the presence of an acidic catalyst.

Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, o-catechol, 4-methylo-catechol, o-cresol, phloroglucinol, styroquinol, and iso-styroquinol. These phenols may be used alone or in combination of two or more.

Specific examples of aldehydes include formaldehyde, trioxane, 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. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

Examples of alkaline-soluble resins include acid-modified epoxy acrylates. Commercially available acid-modified epoxy acrylates include 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 manufactured by Nippon Kayaku Co., Ltd.

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.

The content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 500 to 10,000 parts by mass, and more preferably 1,000 to 7,000 parts by mass, per 100 parts by mass of the fluorinated resin. If the content of the alkali-soluble resin exceeds 10,000 parts by mass, the fluorinated resin of the present invention tends to fail to fully exhibit its ink repellency after UV ozone treatment or oxygen plasma treatment.

If the photosensitive resin composition of the present invention contains a naphthoquinone diazide-containing compound, the barrier ribs obtained from the photosensitive resin composition of the present invention can have a good shape. The naphthoquinone diazide-containing compound is not particularly limited, and naphthoquinone diazide-containing compounds commonly used as photosensitive components of I-ray resist compositions can be used.

Specific examples of naphthoquinonediazide-containing compounds include naphthoquinone-1,2-diazide-4-sulfonate compounds, naphthoquinone-1,2-diazide-5-sulfonate compounds, naphthoquinone-1,2-diazide-6-sulfonate compounds, naphthoquinone-1,2-diazide-sulfonate compounds, o-benzoquinonediazide-sulfonate compounds, and o-anthraquinonediazide-sulfonate compounds. Among these, naphthoquinone-1,2-diazide-4-sulfonate compounds, naphthoquinone-1,2-diazide-5-sulfonate compounds, and naphthoquinone-1,2-diazide-6-sulfonate compounds are preferred due to their excellent solubility. These compounds may be used alone or in combination of two or more.

The content of the naphthoquinonediazide-containing compound in the photosensitive resin composition of the present invention is preferably 10 to 60 parts by weight, and more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the fluorinated resin (wherein, when the photosensitive resin composition includes the aforementioned alkali-soluble resin, this is the total concentration including the alkali-soluble resin). If the content exceeds 60 parts by weight, the sensitivity of the photosensitive resin composition tends to be insufficient.

If the photosensitive resin composition of the present invention contains an alkaline compound, it has the effect of slowing the diffusion rate of the acid generated by the photoacid generator into the film of the photosensitive resin composition of the present invention. By adding the alkaline compound, the acid diffusion distance can be adjusted, thereby improving the shape of the barrier ribs. Furthermore, by adding the alkaline compound, the barrier ribs are less likely to deform even if the time between barrier rib formation and exposure is long, allowing for stable barrier rib formation with the desired precision.

Examples of alkaline compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, and specific examples include secondary or tertiary aliphatic amines and alkanolamines. These alkaline compounds may be used alone or in combination of two or more.

Examples of the aliphatic amines include alkylamines or alkylolamines in which at least one hydrogen atom of ammonia (NH ₃ ) is substituted with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, 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-n-octanolamine. Among them, dialkylamines, trialkylamines, and alkylolamines are preferred, and alkylolamines are more preferred. Among the alkanolamines, triethanolamine and triisopropanolamine are particularly preferred.

Examples of the aromatic amines 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- Aniline derivatives such as dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, 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, 4,4-dimethylaminopyridine, Heterocyclic amines such as methylimidazoline; hindered amines such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-imidodiethanol , 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)piperidinium, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperidinium, 1-[2-(2-hydroxyethoxy)ethyl]piperidinium and the like; picoline, lutidine, pyrrole, piperidine, piperidinium, indole, hexamethylenetetramine, etc.

In the photosensitive resin composition of the present invention, the content of the alkaline compound is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the fluorinated resin (where the photosensitive resin composition contains the aforementioned alkaline-soluble resin, this is the total concentration including the resin). If the amount of the alkaline compound is less than 0.001 parts by mass, the effect as an additive may not be fully achieved. If the amount exceeds 2 parts by mass, the resolution or sensitivity tends to decrease.

The photosensitive resin composition of the present invention may also contain other additives as needed. Examples of such additives include dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, tackifiers, leveling agents, defoaming agents, compatibilizers, adhesion promoters, antioxidants, and other additives. These other additives may be known additives.

Furthermore, as the surfactant, it is preferred to contain one or more of a fluorine-based surfactant or a silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, or a surfactant containing both fluorine atoms and silicon atoms).

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

(1) Film Formation Step: First, after applying the photosensitive resin composition of the present invention onto a substrate, the photosensitive resin composition is heated to form a fluorine-containing resin film. The heating conditions are not particularly limited, but are preferably performed at 80-100°C for 60-200 seconds. This removes solvents and the like contained in the photosensitive resin composition.

Substrates can include silicon wafers, metals, glass, and ITO (Indium Tin Oxides) substrates. Also, organic or inorganic films can be pre-formed on the substrate. For example, an antireflective film or a multi-layered resist base layer can be provided, and a pattern can be formed thereon. Furthermore, the substrate can be pre-cleaned. For example, ultrapure water, acetone, or alcohols (methanol, ethanol, or isopropyl alcohol) can be used for cleaning.

As a method for coating the photosensitive resin composition of the present invention on a substrate, a known method such as spin coating can be used.

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

The exposure dose of high energy rays is preferably 1 mJ/ ^cm2 to 200 mJ/ ^cm2 , more preferably 10 mJ/ ^cm2 to 100 mJ/ ^cm2 .

(3) Development Step Next, the fluorinated resin film after the exposure step is developed with an alkaline aqueous solution to form a fluorinated resin pattern film. That is, the fluorinated resin pattern film is formed by dissolving either the exposed portion or the unexposed portion of the fluorinated resin film in an alkaline aqueous solution.

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

The developing method may be a known method, for example, an immersion method, a liquid coating method, a spray method, etc.

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

After development, a step of washing the fluorinated resin pattern film with deionized water or the like may be optionally provided. The washing method and time are preferably from 10 seconds to 3 minutes, more preferably from 30 seconds to 2 minutes.

The partitions produced in this way can be used as barriers for displays.

The display of the present invention is characterized by comprising a light-emitting element having: partitions comprising the photosensitive resin composition of the present invention; and a light-emitting layer disposed in the regions defined by the partitions. Examples of the display include organic EL displays and quantum dot displays. [Examples]

The present invention is described in detail below with reference to embodiments, but the present invention is not limited to these embodiments.

1. Monomer Synthesis [Synthesis Example 1] Synthesis of 5,5,5-trifluoro-2-methyl-1-pentene-3-yne (TFMPY) To a 500 mL glass flask equipped with a stirrer, 13 g of trans-1-chloro-3,3,3-trifluoropropene (product name: 1233E, manufactured by Central Glass Co., Ltd.) and 50 mL of tetrahydrofuran were added and cooled to -78°C. 100 mL of a 1.6 M n-butyllithium hexane solution was added dropwise and stirred for 30 minutes. Then, 5.81 g of dehydrated acetone was added. After stirring for 1 hour, 100 mL of water was added and the organic layer was separated. The separated organic layer was washed with 100 mL of water three times. The fraction at 99-103°C was then recovered by atmospheric distillation to obtain 5,5,5-trifluoro-2-methyl-3-pentyn-2-ol (hereinafter referred to as TFMPO) (10.5 g) in a 69% yield.

[Chemistry 4] Next, 15 g of concentrated sulfuric acid was added to a 100 ml glass flask equipped with a stirrer. The mixture was heated to 100°C, and then 10 g of TFMPO was slowly added dropwise over 1 hour. After the addition, the mixture was stirred at 100°C for 60 minutes. Analysis of the reaction solution by ¹⁹ F-NMR revealed no residual starting material. The distillate at 68-70°C was then recovered from the reaction solution by atmospheric distillation, yielding 5,5,5-trifluoro-2-methyl-1-pentene-3-yne (hereinafter referred to as TFMPY) in a 55% yield.

[Chemistry 5]

<NMR Analysis Results> ¹ H-NMR (Solvent: Deuterated chloroform, Standard substance: TMS (Tetramethylsilane)); δ (ppm) 1.92 (1H, m) 5.52 (1H, m), 5.85 (1H, m) ¹⁹ F-NMR (Solvent: Deuterated chloroform, Standard substance: C ₆ D ₆ ); δ (ppm) -49.8 (3F, S)

[Synthesis Example 2] Synthesis of 4-Hydroxystyrene (p-HO-St) (Synthesis was performed with reference to the example in Japanese Patent Publication No. 2016-98181) 100 g of 4-acetoxystyrene (Tokyo Chemical 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 at room temperature (approximately 20°C). 0.50 g of 1,3,5-trihydroxybenzene (equivalent to 0.5% by mass of p-AcO-St) was added as a polymerization inhibitor. Next, the solution was cooled to 0°C in an ice bath, and then a 12% by mass aqueous sodium hydroxide solution (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. The reaction solution was analyzed by ^1H -NMR, and no residual raw materials were detected. Next, an 18% by mass aqueous hydrochloric acid solution (equivalent to 0.8 equivalent of p-AcO-St) was added dropwise over 30 minutes, and stirred for 30 minutes after the addition was completed. The pH value of the solution was measured, and the pH value was 6. The obtained reaction solution was extracted with 360 g of methyl tert-butyl ether at room temperature (about 20°C). Next, the solution was washed twice with 330 g of purified water. To the resulting organic layer, 1,3,5-trihydroxybenzene was added at a concentration equivalent to 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 to cause crystallization of the 4-hydroxystyrene. The crystals were separated by filtration and washed with n-octane. The crystals were then dried at 25°C under reduced pressure to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield: 66%).

[Chemistry 6]

2. Preparation of Fluoropolymer (Step 1: Polymerization) [Determination of the Molar Ratio of Monomers Constituting Each Repeating Unit] NMR The molar ratio of monomers constituting each repeating unit in the polymer is determined by ¹ H-NMR, ¹⁹ F-NMR, or ¹³ C-NMR measurements.

[Polymer Molecular Weight Determination] GPC The weight-average molecular weight (Mw) and molecular weight dispersion index (Mw/Mn, the ratio of the number-average molecular weight (Mn) to the weight-average molecular weight (Mw)) of polymers were determined using a high-performance gel permeation chromatography (hereinafter sometimes referred to as GPC; manufactured by Tosoh Corporation, model HLC-8320GPC). An ALPHA-M column and an ALPHA-2500 column (both manufactured by Tosoh Corporation) were connected in series, using tetrahydrofuran (THF) as the developing solvent. A refractive index difference detector was used.

2-1. Polymerization of Fluororesin Precursor [Synthesis of Fluororesin Precursor 1] At room temperature (approximately 20°C), 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) were placed in a 500°C stirring vessel equipped with a stirrer. To a 1.5-ml glass flask, 1.6 g (0.01 mol) of 2,2'-azobis(2-methylbutyronitrile) (Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) was added. The mixture was degassed while stirring, and then the flask was purged with nitrogen. The temperature was raised to 75°C, and the reaction was allowed to proceed 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 isolated by decanting. After drying under reduced pressure at 60°C, 69 g of fluororesin precursor 1 was obtained as a transparent, viscous substance with an 86% yield.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 1, expressed in molar %, is 41:28:31 for the monomer units derived from AN:MA-C4F:HEMA.

[Chemistry 7] Fluorinated resin precursor 1

＜GPC measurement results＞ Mw=6,700, Mw/Mn=1.3

[Synthesis of Fluororesin Producer 2] Fluororesin producer 2, consisting of the following repeating units, was obtained in 85% yield by following the same synthesis procedure as for Fluororesin Producer 1, except that 2-(perfluorohexyl)ethyl methacrylate (Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F) was used instead of MA-C4F.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 2, expressed in molar %, is 42:27:31 for the monomer units derived from AN:MA-C6F:HEMA.

[Chemistry 8] Fluorinated resin precursor 2

＜GPC measurement results＞ Mw=6,300, Mw/Mn=1.3

[Synthesis of Fluororesin Precursor 3] Fluororesin precursor 3, containing the following repeating units, was obtained in 83% yield by following the same synthesis procedure as for Fluororesin Precursor 1, except that methacrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MN) was used instead of AN.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 3, expressed in molar %, is MN-derived monomer units: MA-C4F-derived monomer units: HEMA-derived monomer units = 40:28:32.

[Chemistry 9] Fluorinated resin precursor 3

＜GPC measurement results＞ Mw=4,700, Mw/Mn=1.3

[Synthesis of Fluororesin Producer 4] Fluororesin producer 4, containing the following repeating units, was obtained in 83% yield by following the same synthesis sequence as for Fluororesin Producer 2, except that MN was used instead of AN.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 4, expressed in molar %, is MN-derived monomer units: MA-C6F-derived monomer units: HEMA-derived monomer units = 39:29:32.

[Chemistry 10] Fluorinated resin precursor 4

＜GPC measurement results＞ Mw=4,200, Mw/Mn=1.3

[Synthesis of Fluororesin Producer 5] Fluororesin Producer 5, comprising the following repeating units, was obtained in 80% yield by following the same procedure as for Fluororesin Producer 3-1, except that TFMPY obtained in Synthesis Example 1 was used instead of AN.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 5, expressed in molar %, is TFMPY-derived monomer units: MA-C4F-derived monomer units: HEMA-derived monomer units = 38:30:32.

[Chemistry 11] Fluorinated resin precursor 5

＜GPC measurement results＞ Mw=4,400, Mw/Mn=1.3

[Synthesis of Fluororesin Producer 6] Fluororesin Producer 6, consisting of the following repeating units, was obtained in 81% yield by following the same procedure as for Fluororesin Producer 2, except that TFMPY obtained in Synthesis Example 1 was used instead of AN.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 6, expressed in molar %, is TFMPY-derived monomer units: MA-C6F-derived monomer units: HEMA-derived monomer units = 39:29:32.

[Chemistry 12] Fluorinated resin precursor 6

＜GPC measurement results＞ Mw=4,600, Mw/Mn=1.3

[Synthesis of Fluororesin 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 placed in 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, heated to 75°C, and reacted 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 isolated by decanting. After drying under reduced pressure at 60°C, 74 g of fluororesin precursor 7 was obtained as a transparent viscous substance with a yield of 84%.

<NMR Measurement Results> The composition ratio of the repeating units of fluororesin precursor 7, expressed in molar %, is AN-derived monomer units: MA-C4F-derived monomer units: HEMA-derived monomer units: MAA-derived monomer units = 33:24:26:17.

[Chemistry 13] Fluorinated resin precursor 7

＜GPC measurement results＞ Mw=7,700, Mw/Mn=1.4

[Synthesis of Fluororesin Producer 8] Fluororesin producer 8, consisting of the following repeating units, was obtained in 81% yield by following the same synthesis sequence as fluororesin producer 7, except that MN was used instead of AN and MA-C6F was used instead of MA-C4F.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 8, expressed in molar %, is: monomer unit derived from MN: monomer unit derived from MA-C6F: monomer unit derived from HEMA: monomer unit derived from MAA = 34:23:25:18.

[Chemistry 14] Fluorinated resin precursor 8

＜GPC measurement results＞ Mw=5,300, Mw/Mn=1.3

[Synthesis of Fluororesin Precursor 9] Fluororesin precursor 9, containing the following repeating units, was obtained in 81% yield by following the same synthesis sequence as for Fluororesin Precursor 7, except that MA-C6F was used instead of MA-C4F and acrylic acid (hereinafter referred to as AA) was used instead of MAA.

<NMR Measurement Results> The composition ratio of the repeating units in fluororesin precursor 9, expressed in molar %, is 34:23:27:16 (monomer units derived from AN: monomer units derived from MA-C6F: monomer units derived from HEMA: monomer units derived from AA).

[Chemistry 15] Fluorinated resin precursor 9

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

[Synthesis of Fluororesin Producer 10] Fluororesin producer 10, containing the following repeating units, was obtained in 82% yield by following the same synthesis sequence as fluororesin producer 7, except that MN was used instead of AN and AA was used instead of MAA.

<NMR Measurement Results> The composition ratio of the repeating units in the fluororesin precursor 10, expressed in molar %, is MN-derived monomer units: MA-C4F-derived monomer units: HEMA-derived monomer units: AA-derived monomer units = 33:24:26:17.

[Chemistry 16] Fluorinated resin precursor 10

＜GPC measurement results＞ Mw=5,500, Mw/Mn=1.3

2-2. Comparative Synthesis of Fluororesin Precursors [Comparative Polymerization 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, 84 g of MEK, and 1.6 g (0.010 mol) of AIBN were placed in a 300 ml glass flask equipped with a stirrer. Deaeration was performed while stirring, and the atmosphere in the flask was replaced with nitrogen. The temperature was raised to 80°C, and the reaction was allowed to proceed for 6 hours. The reaction mixture was added dropwise to 500 g of n-heptane, yielding a white precipitate. The precipitate was separated by filtration and dried under reduced pressure at 60°C to yield 55 g of comparative fluorinated resin precursor 1 as a white solid with a yield of 64%.

<NMR Measurement Results> Comparison of the compositional ratios of the repeating units in fluororesin precursor 1, expressed as a molar ratio, revealed that the ratio of monomer units derived from MA-C6F: monomer units derived from HFIP-M: monomer units derived from MAA was 26:20:54.

[Chemistry 17] Comparison of fluorinated resin precursor 1

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

[Comparative Polymerization 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 placed in a 300 ml glass flask equipped with a stirrer. 1.6 g (0.010 mol) of AIBN was added, and the mixture was degassed while stirring. The flask was then purged with nitrogen, heated to 80°C, and reacted for 6 hours. The reaction mixture was then added dropwise to 500 g of n-heptane, yielding a white precipitate. The precipitate was separated by filtration and dried under reduced pressure at 60°C to obtain 60 g of comparative fluorinated resin precursor 2 as a white solid with a yield of 68%.

<NMR Measurement Results> The molar ratio of the repeating units in fluororesin precursor 2 was 24:26:24:26.

[Chemistry 18] Comparison of Fluorinated Resin Precursor 2

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

[Comparative Polymerization 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 (Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as HEVE), and 64 g of MEK were placed in a 300 ml glass flask equipped with a stirrer. 1.6 g (0.010 mol) of AIBN was added, and the mixture was degassed while stirring. The flask was then purged with nitrogen, 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 separated by filtration and dried under reduced pressure at 60°C to obtain 51 g of comparative fluorinated resin precursor 3 as a white solid with a yield of 81%.

<NMR Measurement Results> Comparison of the compositional ratios of the repeating units in fluororesin precursor 3, expressed as a molar ratio, revealed that the ratio of monomer units derived from HEVE: monomer units derived from MA-C6F: monomer units derived from p-HO-St was 35:31:34.

[Chemistry 19] Comparison of Fluorinated Resin Precursor 3

＜GPC measurement results＞ Mw=17,300, Mw/Mn=1.7

3. Production of Fluororesins (Second Step: Addition Reaction) Fluororesins were synthesized by reacting fluororesin precursors 1-6 and comparative fluororesin precursors 1-3 obtained in "2. Production of Fluororesins (First Step: Polymerization)" with an acrylic acid derivative. Karenz-AOI (manufactured by Showa Denko Co., Ltd.) was used as the acrylic acid derivative. This reaction was an addition reaction between the hydroxyl groups in each fluororesin precursor and the acrylic acid derivative.

[Chemistry 20] Karenz-AOI

[Synthesis of Fluororesin 1] 10 g (hydroxyl equivalent weight 0.019 mol) of fluororesin precursor 1 and 20 g of PGMEA were placed in a 300 ml glass flask equipped with a stirrer. 2.68 g (0.019 mol) of Karenz-AOI was added and the mixture was reacted at 45°C for 4 hours. The reaction mixture was concentrated and 150 g of n-heptane was added to allow precipitation. The precipitate was separated by filtration and dried under reduced pressure at 40°C to yield 11.4 g of fluororesin 1 as a white solid in a 90% yield.

< ^13C -NMR Measurement Results> In Fluororesin 1, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from AN and monomer units derived from MA-C4F) was confirmed to be unchanged compared to Fluororesin Prototype 1 (same as before crosslinking group introduction).

[Synthesis of Fluoro-Resin 2] Fluoro-Resin 2 was obtained in 91% yield by following the same synthesis procedure as Fluoro-Resin 1, except that Fluoro-Resin Precursor 2 was used instead of Fluoro-Resin Precursor 1.

< ^13C -NMR Measurement Results> In Fluororesin 2, the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) expressed in a molar ratio of 95:5 were confirmed. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from AN and monomer units derived from MA-C6F) remained unchanged compared to that in Fluororesin Prototype 2 (the same as before crosslinking group introduction).

[Synthesis of Fluoro-Resin 3] Fluoro-Resin 3 was obtained in 90% yield by following the same synthesis procedure as Fluoro-Resin 1, except that Fluoro-Resin Precursor 3 was used instead of Fluoro-Resin Precursor 1.

< ^13C -NMR Measurement Results> In Fluororesin 3, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 97:3. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MN and monomer units derived from MA-C4F) was confirmed to be unchanged compared to Fluororesin Prototype 3 (same as before crosslinking group introduction).

[Synthesis of Fluororesin 4] Fluororesin 4 was obtained in 89% yield by following the same synthesis procedure as Fluororesin 1, except that Fluororesin Precursor 4 was used instead of Fluororesin Precursor 1.

< ^13C -NMR Measurement Results> In fluororesin 4, the molar ratio of the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MN and monomer units derived from MA-C6F) was confirmed to be unchanged compared to that of fluororesin protopolymer 4 (the same as before crosslinking group introduction).

[Synthesis of Fluororesin 5] Fluororesin 5 was obtained in a 92% yield by following the same synthesis procedure as Fluororesin 1, except that Fluororesin Precursor 5 was used instead of Fluororesin Precursor 1.

< ^13C -NMR Measurement Results> In fluororesin 5, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 95:5. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from TFMPY and monomer units derived from MA-C4F) was confirmed to be unchanged compared to that in fluororesin protopolymer 5 (the same as before crosslinking group introduction).

[Synthesis of Fluororesin 6] Fluororesin 6 was obtained in 89% yield by following the same synthesis procedure as Fluororesin 1, except that Fluororesin Precursor 6 was used instead of Fluororesin Precursor 1.

< ^13C -NMR Measurement Results> In fluororesin 6, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from TFMPY and monomer units derived from MA-C6F) was confirmed to be unchanged compared to that in fluororesin protopolymer 6 (the same as before crosslinking group introduction).

[Synthesis of Fluororesin 7] 10 g of fluororesin precursor 7 (alcoholic hydroxyl equivalent 0.018 mol) and 20 g of PGMEA were placed in a 300 ml glass flask equipped with a stirrer. 2.52 g (0.018 mol) of Karenz-AOI was added and the mixture was reacted at 45°C for 5 hours. The reaction mixture was concentrated and 150 g of n-heptane was added to precipitate the product. The precipitate was separated by filtration and dried under reduced pressure at 40°C to yield 12.0 g of fluororesin 7 as a white solid in a 96% yield.

< ^13C -NMR Measurement Results> In fluororesin 7, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual alcoholic hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from AN and monomer units derived from MA-C4F) was confirmed to be unchanged compared to that of fluororesin protopolymer 7 (the same as before crosslinking group introduction).

[Synthesis of Fluororesin 8] Fluororesin 8 was obtained in a 93% yield by following the same synthesis procedure as Fluororesin 7, except that Fluororesin Precursor 8 was used instead of Fluororesin Precursor 7.

< ^13C -NMR Measurement Results> In Fluororesin 8, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual alcoholic hydroxyl groups (unreacted rate) was 97:3. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MN and monomer units derived from MA-C6F) was confirmed to be unchanged compared to Fluororesin Prototype 8 (same as before crosslinking group introduction).

[Synthesis of Fluororesin 9] Fluororesin 9 was obtained in a 90% yield by following the same synthesis procedure as Fluororesin 7, except that Fluororesin Precursor 9 was used instead of Fluororesin Precursor 7.

< ^13C -NMR Measurement Results> In fluororesin 9, the molar ratio of the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 95:5. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from AN and monomer units derived from MA-C6F) was confirmed to be unchanged compared to that of fluororesin protopolymer 9 (the same as before crosslinking group introduction).

[Synthesis of Fluororesin 10] Fluororesin 10 was obtained in a 93% yield by following the same synthesis procedure as Fluororesin 7, except that Fluororesin Precursor 10 was used instead of Fluororesin Precursor 7.

< ^13C -NMR Measurement Results> In fluororesin 10, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MN and monomer units derived from MA-C4F) was confirmed to be unchanged compared to the fluororesin precursor 10 used (same as before crosslinking group introduction).

[Synthesis of Comparative Fluororesin 1] Fluororesin 1 was obtained in 89% yield by following the same synthesis procedure as Fluororesin 1, except that Comparative Fluororesin Precursor 1 was used instead of Fluororesin Precursor 1.

< ^13C -NMR Measurement Results> In Comparative Fluororesin 1, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MA-C6F and monomer units derived from HFIP-M) was confirmed to be unchanged from that in Comparative Fluororesin Prototype 1 (same as before crosslinking group introduction).

[Synthesis of Comparative Fluorine-Containing Resin 2] Comparative Fluorine-Containing Resin 2 was obtained in 90% yield by following the same synthesis procedure as Fluorine-Containing Resin 1, except that Comparative Fluorine-Containing Resin Precursor 2 was used instead of Fluorine-Containing Resin Precursor 1.

< ^13C -NMR Measurement Results> In Comparative Fluororesin 2, the molar ratio of the amount of Karenz-AOI-derived acrylic acid derivative introduced (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 96:4. Furthermore, the composition ratio of the repeating units that do not react with the crosslinking sites (monomer units derived from MA-C6F and monomer units derived from HFIP-M) was confirmed to be unchanged from that in Comparative Fluororesin Prototype 2 (same as before crosslinking group introduction).

[Synthesis of Comparative Fluorine-Containing Resin 3] Comparative Fluorine-Containing Resin 3 was obtained in 90% yield by following the same synthesis procedure as Fluorine-Containing Resin 1, except that Comparative Fluorine-Containing Resin Precursor 3 was used instead of Fluorine-Containing Resin Precursor 1.

< ^13C -NMR Measurement Results> In Comparative Fluororesin 3, the molar ratio of the amount of acrylic acid derivative introduced from Karenz-AOI (reaction rate) to the amount of residual hydroxyl groups (unreacted rate) was 95:5. Furthermore, the composition ratio of the repeating units (monomer units derived from MA-C6F) that do not react with the crosslinking sites was confirmed to be unchanged from that in Comparative Fluororesin Prototype 3 (same as before crosslinking group introduction).

4. Preparation of Photosensitive Resin Composition [Preparation of Photosensitive Resin Composition 1] 0.5 parts by mass of the prepared fluorinated resin 1, 0.5 parts by mass of Irgacure 369 (manufactured by BASF Corporation) as a photopolymerization initiator, 50 parts by mass of pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a crosslinking agent, 50 parts by mass of ZAR2051H (manufactured by Nippon Kayaku Co., Ltd.) as an alkali-soluble resin, and 160 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 70 parts by mass of propylene glycol monomethyl ether (PGME) as solvents were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to prepare photosensitive resin composition 1.

[Preparation of Photosensitive Resin Composition 2] Photosensitive resin composition 2 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 2 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 3] Photosensitive resin composition 3 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 3 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 4] Photosensitive resin composition 4 was prepared using the same procedures as for photosensitive resin composition 1, except that fluorinated resin 4 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 5] Photosensitive resin composition 5 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 5 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 6] Photosensitive resin composition 6 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 6 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 7] Photosensitive resin composition 7 was prepared using the same procedure as for photosensitive resin composition 1, except that fluorinated resin 7 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 8] Photosensitive resin composition 8 was prepared using the same procedure as for photosensitive resin composition 1, except that fluorinated resin 8 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 9] Photosensitive resin composition 9 was prepared using the same procedure as for photosensitive resin composition 1, except that fluorinated resin 9 was used instead of fluorinated resin 1.

[Preparation of Photosensitive Resin Composition 10] Photosensitive resin composition 10 was prepared using the same procedures as for photosensitive resin composition 1, except that fluorinated resin 10 was used instead of fluorinated resin 1.

[Preparation of Comparative Photosensitive Resin Composition 1] Comparative photosensitive resin composition 1 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 1 was used instead of fluorinated resin 1.

[Preparation of Comparative Photosensitive Resin Composition 2] Comparative Photosensitive Resin Composition 2 was prepared following the same procedures as for Photosensitive Resin Composition 1, except that Comparative Fluoropolymer Resin 2 was used instead of Fluoropolymer Resin 1.

[Preparation of Comparative Photosensitive Resin Composition 3] Comparative photosensitive resin composition 3 was prepared following the same procedures as for photosensitive resin composition 1, except that fluorinated resin 3 was used instead of fluorinated resin 1.

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

[Barrier Formation] A 10 cm square ITO substrate was cleaned with ultrapure water and then acetone, then treated with UV ozone for 5 minutes using a UV ozone treatment system (Model: PL17-110, manufactured by SEN Specialty Lighting Co., Ltd.). Next, photosensitive resin compositions 1-10 and comparative photosensitive resin compositions 1-3 obtained in "4. Preparation of Photosensitive Resin Compositions" were applied to the UV ozone-treated substrate using a spin coater at 1,000 rpm. The films were heated on a hot plate at 100°C for 150 seconds to form 2 μm-thick fluororesin and comparative fluororesin films. The resulting resin film was exposed to i-rays (365 nm wavelength) through a mask with 5 μm lines and spaces using a mask alignment and exposure system (SUSS MicroTec Co., Ltd.). The exposed resin film was evaluated for developer solubility, barrier properties (sensitivity, resolution), and contact angle.

[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 barrier solubility was evaluated by measuring the film thickness after immersion using a contact-type film thickness gauge. Complete dissolution of the barrier was considered "soluble," while residual barrier dissolution was considered "insoluble." The results are shown in Table 1.

[Barrier Performance (Sensitivity, Resolution)] The optimal exposure dose (Eop) (mJ/ ^cm² ) for forming the barrier ribs, the line-and-space pattern described above, was determined and used as an indicator of sensitivity. The resulting barrier rib patterns were observed under a microscope to evaluate resolution. No visible edge roughness was rated "Excellent," slight visible edge roughness was rated "Good," and significant edge roughness was rated "Unacceptable." The results are shown in Table 1.

[Table 1] barrier 1 2 3 4 5 6 7 8 9 10 Comparison 1 Comparison 2 Comparison 3 Photosensitive resin composition 1 2 3 4 5 6 7 8 9 10 Comparison 1 Comparison 2 Comparison 3 Developer solubility Unexposed part Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Exposure Department Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Barrier performance Sensitivity (mJ/cm ² ) 102 105 102 102 100 102 100 102 102 102 105 102 100 resolution Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent

[Contact Angle] The substrates with barrier ribs obtained through the above steps were heated at 230°C for 60 minutes. The entire surface of the substrates was then subjected to UV ozone treatment or oxygen plasma treatment for 10 minutes. Subsequently, the substrates were heated at 230°C for 60 seconds. Before and after the UV ozone or oxygen plasma treatment, and after the subsequent heating step, the contact angles of the barrier rib surfaces with respect to anisole, PGMEA, and water were measured using a contact angle meter (DMs-601, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 2. The UV ozone treatment apparatus used was the same as that described above. In addition, a plasma dry cleaner PDC210 manufactured by Yamato Scientific Co., Ltd. was used as an oxygen plasma treatment device. Oxygen plasma treatment was performed at an oxygen flow rate of 30 cc/min and an output of 300 W.

[Table 2] barrier 1 2 3 4 5 6 7 8 9 10 Comparison 1 Comparison 2 Comparison 3 Photosensitive resin composition 1 2 3 4 5 6 7 8 9 10 Comparison 1 Comparison 2 Comparison 3 PGMEA contact angle (°) Unexposed part Before UV ozone treatment 30 31 33 29 28 28 27 28 27 26 31 29 27 After UV ozone treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 PGMEA contact angle (°) exposure part Before UV ozone treatment 42 45 43 45 42 44 42 44 45 43 44 44 44 After UV ozone treatment 25 twenty three twenty four twenty one twenty two twenty four twenty one 19 20 20 25 25 twenty three After the heating step 40 43 41 44 40 44 41 44 43 43 twenty one twenty two 20 Anisole contact angle (°) Unexposed area Before UV ozone treatment 33 35 30 37 35 36 32 33 31 32 39 37 37 After UV ozone treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 Anisole contact angle (°) Exposure area Before UV ozone treatment 69 71 68 70 69 70 67 65 66 65 71 70 70 After UV ozone treatment 50 53 51 48 51 47 43 42 46 48 45 44 42 After the heating step 67 70 67 70 68 69 67 65 65 64 34 35 32 Water contact angle (°) Unexposed part Before UV ozone treatment 102 108 105 108 103 109 98 101 96 103 107 108 105 After UV ozone treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 Water contact angle (°) Exposure part Before UV ozone treatment 103 110 106 110 106 109 107 109 107 106 109 109 107 After UV ozone treatment 60 62 58 63 62 65 55 58 54 56 60 65 56 After the heating step 104 108 106 110 106 108 106 108 106 106 53 50 48 PGMEA contact angle (°) Unexposed part Before oxygen plasma treatment 31 31 33 29 28 30 30 27 28 27 28 30 29 After oxygen plasma treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 PGMEA contact angle (°) exposure part Before oxygen plasma treatment 43 46 41 44 42 43 42 44 45 43 45 44 44 After oxygen plasma treatment 26 25 26 twenty three 27 25 twenty two 20 20 twenty two 27 twenty four 28 After the heating step 42 44 41 43 40 42 42 43 43 43 twenty two 20 twenty four Anisole contact angle (°) Unexposed area Before oxygen plasma treatment 32 34 32 35 34 36 31 32 31 31 37 37 36 After oxygen plasma treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 Anisole contact angle (°) Exposure area Before oxygen plasma treatment 70 70 69 71 70 68 66 64 67 66 70 71 71 After oxygen plasma treatment 51 51 53 50 49 48 44 43 42 44 44 42 43 After the heating step 68 69 69 70 69 66 65 63 66 66 31 32 30 Water contact angle (°) Unexposed part Before oxygen plasma treatment 105 108 104 110 105 107 98 101 97 102 108 106 106 After oxygen plasma treatment 10 10 10 10 10 10 10 10 10 10 10 10 10 After the heating step 10 10 10 10 10 10 10 10 10 10 10 10 10 Water contact angle (°) Exposure part Before oxygen plasma treatment 104 109 103 108 103 109 106 110 108 107 108 109 107 After oxygen plasma treatment 59 60 60 61 62 64 55 56 53 55 61 63 58 After the heating step 102 108 101 107 103 109 106 109 108 106 50 51 50

As shown in Table 1, both the barrier ribs of the present invention and the comparative barrier ribs are negative resists, dissolving only in the unexposed areas in the developer solubility evaluation. In the barrier rib performance evaluation, they exhibited comparable sensitivity. 5 μm lines and spaces on the photomask were transferred with excellent resolution, and no line edge roughness was observed, resulting in an "Excellent" resolution. These evaluations demonstrate that the fluorinated resin of the present invention has a smaller impact on the barrier ribs than the comparative fluorinated resin.

On the other hand, as shown in Table 2, the contact angles of the exposed portion (equivalent to the barrier rib top surface) of the barrier rib of the present invention with respect to anisole, PGMEA, and water, while reduced by UV ozone or oxygen plasma treatment, were increased by the subsequent heating step, demonstrating excellent liquid repellency. In the comparative barrier rib, the contact angle was reduced by UV ozone or oxygen plasma treatment, but remained relatively low, with little change even after the subsequent heating step.

Claims (15)

A fluorine-containing resin characterized by comprising a monomer (A) having a triple bond in the side chain as a repeating unit (U) of the monomer unit; and a fluorine atom content of 50% by mass or less. The fluorine-containing resin of claim 1, wherein the fluorine atom content is 5% by mass or greater. The fluorinated resin of claim 1 or 2, wherein at least a portion of the side chains of the monomer (A) contain fluorine atoms. The fluorinated resin of claim 1 or 2, wherein at least a portion of the triple bonds are carbon-nitrogen triple bonds of nitrile groups. The fluorinated resin of claim 1 or 2, wherein at least a portion of the monomer (A) has a structure represented by the following formula (1) or formula (1'): CH ₂ =C(R ¹ )C≡CR ² ･･･(1)CH ₂ =C(R ¹ )XC≡CR ² ･･･(1') (In formula (1) and formula (1'), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, and represents a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted by a hydroxyl group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted by fluorine atoms. The fluorinated resin of claim 5, wherein the structure represented by the above formula (1) or (1') is a structure represented by the following formula (2) or (2'): CH ₂ =C(R ¹ )C≡CR ^f ･･･(2)CH ₂ =C(R ¹ )XC≡CR ^f ･･･(2') (In formula (2) and formula (2'), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted by a hydroxyl group or -OC(=O)-CH ₃ ; R ^f represents a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms). The fluorinated resin of claim 1 or 2, wherein the repeating unit (U) comprises the monomer (A) and a monomer (B) having a structure represented by the following formula (3) or (3') as a monomer unit: CH ₂ =C(R ¹ )COOR ² ･･･(3)CH ₂ =C(R ¹ )COOXR ² ･･･(3') (in formula (3) and (3'), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted by a hydroxyl group or -OC(=O)-CH ₃ ; R ² represents a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group may be substituted by fluorine atoms. The fluorinated resin of claim 7, wherein the structure represented by the above formula (3) or formula (3') is a structure represented by the following formula (4) or formula (4'): _CH2 =C( ^R1 ) ^COORf ･･･(4) _CH2 =C( ^R1 )COOXRf ^･ ･･(4') (in formula (4) and formula (4'), ^R1 represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, representing a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms, or 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted by a hydroxyl group or -OC(=O) _-CH3 ; ^Rf represents a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms). A repellent comprising the fluorine-containing resin according to any one of claims 1 to 8. A photosensitive resin composition is characterized by comprising at least the fluorine-containing resin according to any one of claims 1 to 8, a solvent, and a photopolymerization initiator. The photosensitive resin composition of claim 10 further comprises a crosslinking agent and an alkali-soluble resin. The photosensitive resin composition of claim 10 or 11, which is used to form partition walls. A cured product is characterized in that it is formed by curing the photosensitive resin composition according to any one of claims 10 to 12. A display device is characterized by comprising a light-emitting element, wherein the light-emitting element comprises: a partition wall comprising the hardened material as claimed in claim 13; and a light-emitting layer disposed in an area divided by the partition wall. The display of claim 14, which is an organic EL display or a quantum dot display.