Fluorine-containing resins, liquid repellents, photosensitive resin compositions, cured products, and displays

Abstract

The present invention provides a fluororesin that can be used to create banks (partitions) whose liquid-repellent properties do not deteriorate easily even after UV ozone treatment or oxygen plasma treatment. [Solution] The fluororesin of the present invention is characterized by containing repeating units (U) which include monomers (A) having triple bonds in their side chains as monomer units.

Description

Technical Field

[0001] The present disclosure relates to a fluororesin, a liquid repellent, a photosensitive resin composition, a cured product, and a display.

Background Art

[0002] When manufacturing display elements such as organic EL displays, micro-LED displays, and quantum dot displays, an inkjet method is known as a method for forming an organic layer having functions such as light emission. There are several inkjet methods. Specifically, there are methods such as solidifying ink dropped from a nozzle into a recess of a pattern film having irregularities formed on a substrate, or a method of dropping ink droplets onto a pattern film previously formed on a substrate as a lyophilic part where the ink wets and a liquid repellent part where the ink bounces, and attaching the ink only to the lyophilic part.

[0003] Particularly, in the method of solidifying ink dropped from a nozzle into the recesses of the pattern film mentioned above, mainly two methods can be adopted to produce such a pattern film having irregularities. One is a photolithography method in which the surface of a photosensitive resist film coated on a substrate is exposed in a pattern to form exposed and unexposed parts, and one of the parts is dissolved and removed with a developer. The other is an imprint method using printing technology. After forming a pattern film having irregularities, it is common to perform UV ozone treatment or oxygen plasma treatment on the entire surface of the substrate. By this UV ozone treatment or oxygen plasma treatment, particularly the remaining organic substances in the recesses of the pattern film can be removed, and uneven wetting of the dropped ink can be reduced, thereby preventing defects in the display element.

[0004] The convex portions of the formed pattern film having irregularities are called banks (partition walls). The bank functions as a barrier to prevent the inks from mixing when the ink is dropped into the recesses of the pattern film. In order to enhance this barrier effect, it is required that the substrate surface is exposed in the recesses of the pattern film, the substrate surface is lyophilic to the ink, and the upper surface of the bank is liquid repellent to the ink.

[0005] Fluorine-containing resins are used as the resin for forming such banks. Using fluorine-containing resins improves liquid repellency.

[0006] Patent Document 1 discloses a resist composition containing a fluororesin, comprising a fluororesin (A) having monomer units formed from a monomer represented by formula 1 and having a fluorine atom content of 7 to 35% by mass, and a photosensitive component that reacts to light with a wavelength of 100 to 600 nm, wherein the ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass, and the photosensitive component comprises a photoacid generator (B), an alkali-soluble resin (C) having a carboxyl group and / or a phenolic hydroxyl group, and an acid crosslinking agent (D) which is a compound having two or more groups that can react with a carboxyl group or a phenolic hydroxyl group by the action of an acid. CH2=C(R 1 )COOXR f ...Formula 1 In formula 1, R 1 X represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R represents an organic group with 1 to 6 carbon atoms that does not contain a divalent fluorine atom. f This represents a perfluoroalkyl group having 4 to 6 carbon atoms.

[0007] Patent Document 2 discloses an ink-repellent agent comprising a polymer having a polymerization unit containing a fluorine atom, the polymer having a polymerization unit (b1) having an alkyl group having 20 or fewer carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (however, the alkyl group includes those having etheric oxygen), and a polymerization unit (b2) having an ethylenically double bond, characterized in that the fluorine content is 5 to 25% by mass and the number average molecular weight is 500 or more and less than 10,000.

[0008] Patent Document 3 discloses a resist composition containing a fluororesin, comprising a fluororesin (A) having monomer units formed from a monomer represented by formula 1, having an ethylenically double bond, and having a fluorine atom content of 7 to 35% by mass, and a photosensitive component that reacts to light with a wavelength of 100 to 600 nm, wherein the ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass, and the photosensitive component comprises a photoradical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenically double bonds in one molecule. CH2=C(R 1 )COOXR f ...Formula 1 In formula 1, R 1 X represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R represents an organic group with 1 to 6 carbon atoms that does not contain a divalent fluorine atom. f This represents a perfluoroalkyl group having 4 to 6 carbon atoms.

[0009] Patent Document 4 discloses a negative-type photosensitive resin composition containing a fluorine atom-containing ink-repellent agent, comprising 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 a fluorine atom-containing ink-repellent agent (E), wherein the content of the fluorine atom in the ink-repellent agent (E) is 1 to 40% by mass, and the ink-repellent agent (E) has an ethylenically active double bond.

[0010] Patent Document 5 discloses a photosensitive resin composition having good liquid repellency, comprising at least a fluororesin having crosslinked portions, a solvent, and a photopolymerization initiator, wherein the fluororesin contains repeating units made of hydrocarbons having fluorine atoms. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Patent No. 4474991 [Patent Document 2] Patent No. 4488098 [Patent Document 3] Patent No. 4905563 [Patent Document 4] Patent No. 6536578 [Patent Document 5] International Publication No. 2020 / 110793 [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] When banks (partitions) were fabricated using the resist compositions described in Patent Documents 1 to 4, the cured resin product had excellent liquid repellency, but there was a problem that the liquid repellency decreased when subjected to the aforementioned UV ozone treatment or oxygen plasma treatment.

[0013] The object of this disclosure is to provide a fluororesin that can be used to create banks (partitions) whose liquid-repellent properties do not deteriorate even after UV ozone treatment or oxygen plasma treatment. [Means for solving the problem]

[0014] In light of the above-mentioned problems, the inventors conducted thorough research. As a result, they discovered that the above problems can be solved by using a monomer having a triple bond in its side chain, leading to this disclosure.

[0015] By using the fluororesin disclosed herein, it is possible to create banks (partitions) whose liquid-repellent properties do not deteriorate even after UV ozone treatment or oxygen plasma treatment.

[0016] In other words, this disclosure is as follows:

[0017] The fluororesin of this disclosure is characterized by containing repeating units (U) which include monomers (A) having triple bonds in their side chains as monomer units.

[0018] The fluororesin of the present disclosure preferably has a fluorine atom content of 5% by mass or more.

[0019] The fluororesin of the present disclosure preferably contains fluorine atoms in the side chains of at least a part of the above monomer (A).

[0020] In the fluororesin of the present disclosure, at least a part of the triple bonds are preferably carbon-nitrogen triple bonds of nitrile groups.

[0021] In the fluororesin of the present disclosure, at least a part of the above monomer (A) preferably has a structure represented by the following formula (1) or formula (1´). CH2=C(R 1 )C≡CR 2 ···(1) CH2=C(R 1 )XC≡CR 2 ···(1´) (In 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 alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O)-CH3. R 2 represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cyclic alkyl group having 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.)

[0022] In the fluororesin of the present disclosure, the structure represented by the above formula (1) or (1´) is preferably a structure represented by the following formula (2) or formula (2´). CH2=C(R 1 )C≡CR f ···(2) CH2=C(R 1 )XC≡CR f ···(2´) (In formula (2) and formula (2´), R 1represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, where any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. f (This represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.)

[0023] The fluororesin of this disclosure preferably contains, as monomer units, the repeating unit (U) above includes the monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3'). CH2=C(R 1 )COOR 2 ...(3) CH2=C(R 1 )COOXR 2 ...(3') (In equations (3) and (3'), R 1 represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, where any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. 2 (This represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, where any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.)

[0024] The fluororesin containing the present disclosure preferably has a structure represented by formula (4) or formula (4') below, rather than the structure represented by formula (3) or formula (3') above. CH2=C(R 1 )COOR f ...(4) CH2=C(R 1 )COOXR f ...(4') (In equations (4) and (4'), R 1represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, where any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. f (This represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.)

[0025] The liquid repellent agent of this disclosure is characterized by containing the fluororesin described above.

[0026] The photosensitive resin composition of this disclosure is characterized by comprising at least the fluororesin contained herein, a solvent, and a photopolymerization initiator.

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

[0028] The photosensitive resin composition of this disclosure is preferably used for forming partitions.

[0029] The cured product of this disclosure is characterized by being obtained by curing the photosensitive resin composition of this disclosure described above.

[0030] The display in this disclosure is A partition made of the cured product of the above disclosure, The light-emitting element is characterized by comprising a light-emitting layer disposed in a region partitioned by the above-mentioned partition wall.

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

[0032] According to this disclosure, it is possible to create banks (partitions) whose liquid-repellent properties do not deteriorate even after UV ozone treatment or oxygen plasma treatment. [Modes for carrying out the invention]

[0033] The present disclosure will be described in detail below, but the description of the constituent elements described below is an example of an embodiment of the present disclosure and is not limited to these specific contents. It can be implemented in various ways within the scope of its gist.

[0034] In the "Modes for Carrying Out the Invention" section of this specification, the symbols "[" and "]", "<" and ">" are merely symbols and have no meaning in themselves. In this specification, "polymer" and "resin" are synonymous and, unless otherwise noted, refer to high-molecular-weight compounds.

[0035] In this specification, "bank" and "partition" are synonymous, and unless otherwise noted, they refer to the raised portion of a patterned film with uneven surfaces in an inkjet process.

[0036] (Contains fluororesin) The fluororesin of this disclosure is characterized by containing repeating units (U) which include monomers (A) having triple bonds in their side chains as monomer units.

[0037] By using the fluororesin described herein, banks (partitions) with sufficiently high liquid repellency can be fabricated. Furthermore, the fabricated banks (partitions) are less likely to experience a decrease in liquid repellency even after UV ozone treatment or oxygen plasma treatment. The reason why it is possible to create banks (septaments) with sufficiently high liquid-repellent properties is predicted to be as follows: First, when fluorine-containing alkyl groups segregate on the surface, the liquid-repellent properties improve. As described later, when a bank (partition) is fabricated using the fluororesin of this disclosure, a pattern film is formed, followed by UV ozone treatment or oxygen plasma treatment, and then heat treatment. After forming a patterned film using the fluororesin disclosed herein, UV ozone treatment or oxygen plasma treatment is performed, causing the π electrons of the triple bond to interact with the -CH, -OH, and -NH bonds, thereby immobilizing these functional groups. On the other hand, fluororesin alkyl groups, which have a weak interaction with the π electrons of the triple bond, tend to segregate on the surface. Subsequent heating is thought to promote rearrangement and improve liquid repellency.

[0038] In this specification, "monomer (A) having a triple bond in its side chain" means a monomer that has a triple bond at a position that becomes the side chain of a polymer when monomer (A) forms a polymer. In this specification, "repeating unit (U)" means a monomer unit that constitutes the main chain of a fluororesin, and refers to multiple monomer units present in the main chain. The repeating units (U) may constitute the main chain of the fluororesin in a continuous manner, or other monomer units may be present between the repeating units (U) in the main chain. Furthermore, monomer units other than repeating units (U) may be present at the ends of the main chain of the fluororesin.

[0039] The fluororesin contained in this disclosure preferably has a fluorine atom content of 5% by mass or more. Furthermore, the fluorine atom content is preferably 50% by mass or less. If the fluorine atom content is 5% by mass or more, a bank with even higher liquid repellency can be produced.

[0040] In this specification, "fluorine atom content of fluororesin" refers to a value calculated from the molar ratio of monomers constituting the fluororesin, the molecular weight of monomers constituting the fluororesin, and the fluorine content contained in the monomers, as measured by NMR (nuclear magnetic resonance spectroscopy). Here, we will explain a method for measuring the fluorine content when the fluorine-containing resin is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate. (i) First, the proportion of each component is calculated (molar ratio) by measuring the fluororesin using NMR. (ii) Multiply the molecular weight (Mw) of each monomer in the composition of the fluororesin by its molar ratio, add the resulting values ​​together, and obtain the total value. Calculate the weight percentage (wt%) of each composition from this total value. The molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 1,1-bistrifluoromethylbutadiene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432. (iii) Next, the fluorine content in the monomer is calculated for the fluorine-containing composition. (iv) Calculate the "fluorine content in monomer ÷ monomer molecular weight (Mw) × weight percentage (wt%)" for each component, and sum the obtained values. (v) Calculate the fluorine atom content of the fluororesin by dividing the value obtained in (iv) above by the total value obtained in (ii) above.

[0041] In the fluororesin of this disclosure, it is preferable that at least some monomers (A) have a structure represented by the following formula (1) or formula (1'). CH2=C(R 1 )C≡CR 2 ...(1) CH2=C(R 1 )XC≡CR 2 ...(1') (In equations (1) and (1'), R 1 represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, where any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. 2 (This represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, where any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.)

[0042] Furthermore, in the fluororesin present disclosure, the structure represented by formula (1) or (1') above is preferably the structure represented by formula (2) or (2') below. CH2=C(R 1 )C≡CR f ...(2) CH2=C(R 1 )XC≡CR f ...(2') (In equations (2) and (2'), R 1 represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, where any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3. f (This represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.)

[0043] Preferred structures of formulas (1) and (1') (including preferred structures of formulas (2) and (2')) include the structures represented by the following formulas (1-1) to (1-4) and (2-1) to (2-4).

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

[0045] Furthermore, in the fluororesin of this disclosure, it is preferable that the repeating unit (U) includes the above monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3') as monomer units.

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

[0047] Furthermore, the monomers represented by formulas (3) and (3') preferably have the structures represented by the following formulas (4) and (4').

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

[0049] Equations (4) and (4') are more preferable to the structures shown in the following equations (4'-1) to (4'-3).

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

[0051] If the repeating unit (U) of the fluororesin disclosed herein includes two or more other types of structures represented by formulas (1), (1'), (2), (2'), (3), (3'), (4), and (4'), R 1 , R 2 , R f And X may be the same or different in each structure.

[0052] In the fluororesins of this disclosure, it is preferable that at least some of the side chains of monomer (A) contain fluorine atoms. Furthermore, the fluorine atom may be positioned as a side chain in the structure represented by formula (1), formula (1'), formula (2), or formula (2') above, or it may be positioned as a side chain in other structures.

[0053] In the fluororesin disclosed herein, it is preferable that at least a portion of the triple bond is a carbon-nitrogen triple bond of a nitrile group. Furthermore, the fluorine atom may be positioned as a side chain in the structure represented by formula (1), formula (1'), formula (2), or formula (2') above, or it may be positioned as a side chain in other structures.

[0054] The molecular weight of the fluororesin in this disclosure is the mass-average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as the standard substance, preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and particularly preferably 3,000 or more and 100,000 or less. If the molecular weight is less than 1,000, the strength of the formed fluororesin film or organic EL bank tends to decrease, and if the molecular weight is greater than 1,000,000, solubility in the solvent is insufficient, making it difficult to form a fluororesin film by coating.

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

[0056] The fluororesin contained herein can be used in liquid repellents and photosensitive resin compositions.

[0057] (Photosensitive resin composition) The photosensitive resin composition of this disclosure is characterized by comprising at least the fluororesin contained herein, a solvent, and a photopolymerization initiator.

[0058] The photosensitive resin composition of this disclosure can be used to form banks (partitions). Because it contains the fluororesin described above, it is possible to produce banks (partitions) with sufficiently high liquid repellency. Furthermore, the liquid repellency of the produced banks (partitions) does not easily decrease even when subjected to UV ozone treatment or oxygen plasma treatment.

[0059] The solvent included in the photosensitive resin composition of this disclosure is not particularly limited as long as the fluororesin is soluble, but examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorinated solvents. These may be used individually or in combination of two or more.

[0060] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexisanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

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

[0062] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0063] 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.

[0064] Examples of fluorinated solvents include chlorofluorocarbons (CFCs), alternative CFCs, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0065] In addition, to improve coating properties, high-boiling point weak solvents such as turpentine-based petroleum naphtha solvents or paraffin-based solvents can be used.

[0066] Among them, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate It is preferable that the substance is at least one selected from the group consisting of tate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. It is more preferable that the substance 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.

[0067] The amount of solvent in the photosensitive resin composition of this disclosure is preferably in the range of 50 parts by mass or more and 2,000 parts by mass or less per 100 parts by mass of the concentration of the fluororesin (however, if the photosensitive resin composition contains the alkali-soluble resin described later, this refers to the combined concentration of that resin). More preferably, it is between 100 parts by mass and 1,000 parts by mass or less. By adjusting the amount of solvent, the thickness of the formed resin film can be adjusted, and within the above range, a resin film thickness particularly suitable for obtaining an organic EL bank can be obtained.

[0068] The photopolymerization initiator included in the photosensitive resin composition of this disclosure is not particularly limited as long as it polymerizes monomers having polymerizable double bonds using high-energy rays such as electromagnetic waves or electron beams, and known photopolymerization initiators can be used. As photopolymerization initiators, photoradical initiators or photoacid initiators can be used. These may be used alone, in combination, or as a mixture of two or more photoradical initiators or photoacid initiators. In addition, by using additives in combination with the photopolymerization initiator, living polymerization may be carried out in some cases, and known additives can be used.

[0069] Photoradical initiators can be specifically classified into intramolecular cleavage types, which generate radicals by cleaving intramolecular bonds through absorption by electromagnetic waves or electron beams, and hydrogen abstraction types, which generate radicals by using hydrogen donors such as tertiary amines or ethers in combination. Any of these may be used. Other types of photoradical initiators may also be used.

[0070] Examples of photoradical initiators include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based compounds.

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

[0072] Examples of acetophenone derivatives include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0073] Examples of diketone compounds include 4,4'-dimethoxybenzyl, methyl benzoylmate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylmate are preferred.

[0074] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0075] Examples of quinone compounds include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0076] Examples of acyloin derivatives include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

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

[0078] Among commercially available photoradical initiators, preferred products include those manufactured by BASF Co., Ltd.: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Lugacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, and Lucilin TPO. Of these, Irgacure 651 and Irgacure 369 are more preferred.

[0079] Specifically, the photoacid initiator is an onium salt consisting of a pair of at least one cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxantonium, and (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. Among these, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0080] Examples of commercially available photoinitiators include: Sunapro Co., Ltd.'s product names: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S; Dow Chemical Japan Ltd.'s product names: Cyracure Photoinitiator UVI-6990, Cyracure Photoinitiator UVI-6992, Cyracure Photoinitiator UVI-6976; and ADEKA Corporation's product names: ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, ADEKA Optomer Examples include MARS SP-172, ADEKA Optomer SP-300, CI-5102 and CI-2855 from Nippon Soda Co., Ltd., SunAid SI-60L, SunAid SI-80L, SunAid SI-100L, SunAid SI-110L, SunAid SI-180L, SunAid SI-110, and SunAid SI-180 from Sanshin Chemical Industry Co., Ltd., EsaCure 1064 and EsaCure 1187 from Lamberti, and Irgacure 250 from BASF Co., Ltd.

[0081] The content of the photopolymerization initiator in the photosensitive resin composition of this disclosure is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the fluororesin (however, if the photosensitive resin composition contains the alkali-soluble resin described later, the combined concentration of that resin is also included). If the content of the photopolymerization initiator is less than 0.1 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and if it exceeds 30 parts by mass, the resolution and sensitivity tend to decrease.

[0082] In addition to the essential components of a fluororesin, solvent, and photopolymerization initiator, the photosensitive resin composition of this disclosure may also contain a crosslinking agent, an alkali-soluble resin, a naphthoquinone diazide group-containing compound, a basic compound, and other additives.

[0083] The crosslinking agent contained in the photosensitive resin composition of this disclosure reacts with the repeating units (U) of the fluororesin, allowing the resin to adopt a crosslinked structure and improving the mechanical strength of the resulting film.

[0084] Known crosslinking agents can be used, specifically, compounds obtained by reacting amino group-containing compounds such as melamine, acetoganamine, benzoguanamine, urea, ethylene urea, propylene urea, and glycoluryl with formaldehyde or a lower alcohol, and substituting the hydrogen atoms of the amino group with a hydroxymethyl group or a lower alkoxymethyl group; polyfunctional epoxy compounds; polyfunctional oxetane compounds; polyfunctional isocyanate compounds; and polyfunctional acrylate compounds. Here, those using melamine are called melamine-based crosslinking agents, those using urea are called urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are called alkylene urea-based crosslinking agents, and those using glycoluryl are called glycoluryl-based crosslinking agents. These crosslinking agents may be used individually or in combination of two or more.

[0085] The crosslinking agent is preferably at least one selected from these crosslinking agents, with glycoluryl-based crosslinking agents and polyfunctional acrylate compounds being particularly preferred.

[0086] Examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine, with hexamethoxymethylmelamine being preferred among them.

[0087] Examples of urea-based crosslinking agents include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, with bismethoxymethylurea being the preferred choice.

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

[0089] Examples of glycoluryl crosslinking agents include mono, di, tri and / or tetrahydroxymethylated glycoluryl, mono, di, tri and / or tetramethoxymethylated glycoluryl, mono, di, tri and / or tetraethoxymethylated glycoluryl, mono, di, tri and / or tetrapropoxymethylated glycoluryl, and mono, di, tri and / or tetrabutoxymethylated glycoluryl.

[0090] Examples of polyfunctional acrylate compounds include polyfunctional acrylates (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP), polyethylene glycol diacrylate (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: A-200, A-400, A-600), urethane acrylates (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), and pentaerythritol tetraacrylate.

[0091] The following are examples of preferred polyfunctional acrylate compounds.

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] The crosslinking agent content in the photosensitive resin composition of this disclosure is preferably 10 parts by mass or more and 300 parts by mass or less, and more preferably 50 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of the fluororesin (however, if the photosensitive resin composition contains the alkali-soluble resin described later, the combined concentration of that resin is also included). If the crosslinking agent content is less than 10 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and if it exceeds 300 parts by mass, the resolution and sensitivity tend to decrease.

[0096] If the photosensitive resin composition of this disclosure includes an alkali-soluble resin, the shape of the bank obtained from the photosensitive resin composition of this disclosure can be improved.

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

[0098] Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol. These phenols may be used individually or in combination of two or more types.

[0099] Examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethyl sulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used individually or in combination of two or more types.

[0100] Other examples of alkali-soluble resins include acid-modified epoxy acrylates. Commercially available acid-modified epoxy acrylates include, for example, products from Nippon Kayaku Co., Ltd., such as CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H.

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

[0102] The content of the alkali-soluble resin in the photosensitive resin composition of this disclosure is preferably 500 parts by mass or more and 10,000 parts by mass or less, and more preferably 1,000 parts by mass or more and 7,000 parts by mass or less, per 100 parts by mass of the fluororesin. If the content of the alkali-soluble resin exceeds 10,000 parts by mass, the liquid repellency of the fluororesin of this disclosure to ink after UV ozone treatment or oxygen plasma treatment tends not to be sufficiently obtained.

[0103] If the photosensitive resin composition of this disclosure contains a naphthoquinone diazide group-containing compound, the shape of the bank obtained from the photosensitive resin composition of this disclosure can be improved. The naphthoquinone diazide group-containing compound is not particularly limited, and any compound commonly used as a photosensitive component in i-ray resist compositions can be used.

[0104] Examples of naphthoquinone diazide group-containing compounds include naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds, naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid ester compounds, and orthanthraquinone diazide sulfonic acid ester compounds. Among these, naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, and naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds are preferred due to their excellent solubility. These compounds may be used individually or as a mixture of two or more.

[0105] The content of the naphthoquinone diazide group-containing compound in the photosensitive resin composition of this disclosure is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, per 100 parts by mass of the fluororesin (however, if the photosensitive resin composition contains the aforementioned alkali-soluble resin, the combined concentration of that resin is also included). If the content exceeds 60 parts by mass, it tends to become difficult to obtain the sensitivity of the photosensitive resin composition.

[0106] When the photosensitive resin composition of this disclosure contains a basic compound, the acid generated from the photoacid generator slows down the diffusion rate when it diffuses into the film of the photosensitive resin composition of this disclosure. By incorporating basic compounds, the acid diffusion distance can be adjusted, and the bank shape can be improved. Furthermore, by incorporating basic compounds, the bank becomes less prone to deformation even if the curing time between bank formation and exposure is long, allowing for the stable formation of banks with the desired precision.

[0107] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, specifically secondary or tertiary aliphatic amines and alkyl alcohol amines. These basic compounds may be used individually or in combination of two or more.

[0108] Aliphatic amines include alkylamines or alkyl alcoholamines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di- Examples include n-nonylamine, di-n-decanylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decanylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, with alkyl alcoholamines being more preferred. Among alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0109] Aromatic amines and heterocyclic amines include, for example, aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc., heterocyclic amines such as 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,8-diazabicyclo[5.4.0]unde-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, bis(1,2,2, Examples include hindered amines such as 6,6-pentamethyl-4-piperidyl) sevagate, 2-hydroxypyridine, aminocresol, 2,4-quinoline diol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, and other alcoholic nitrogen-containing compounds, as well as picoline, lutidine, pyrrole, piperidine, piperazine, indole, and hexamethylenetetramine.

[0110] In the photosensitive resin composition of this disclosure, the content of the basic compound is preferably 0.001 parts by mass to 2 parts by mass, and more preferably 0.01 parts by mass to 1 part by mass, per 100 parts by mass of the fluororesin (however, if the photosensitive resin composition contains the aforementioned alkali-soluble resin, the combined concentration of that resin). If the amount of basic compound is less than 0.001 parts by mass, it becomes difficult to obtain sufficient effect as an additive, and if it exceeds 2 parts by mass, there is a tendency for resolution and sensitivity to decrease.

[0111] The photosensitive resin composition of this disclosure may contain other additives as needed. Examples of other additives include dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesives, and antioxidants. These other additives may be known ones.

[0112] Furthermore, it is preferable that the surfactant contains either a fluorine-based surfactant or a silicone-based surfactant (a surfactant containing both a fluorine atom and a silicon atom), or two or more of these.

[0113] Next, a method for forming a partition using the photosensitive resin composition of this disclosure will be described. The method for forming the partition wall may include (1) a film formation step, (2) an exposure step, and (3) a development step. Each step is explained below.

[0114] (1) Film formation process First, the photosensitive resin composition described above is applied to a substrate and then heated to form a fluororesin film containing the photosensitive resin composition. The heating conditions are not particularly limited, but are preferably 80-100°C for 60-200 seconds. This makes it possible to remove solvents and other substances contained in the photosensitive resin composition.

[0115] The substrate can be made of silicon wafer, metal, glass, ITO substrate, or the like. Furthermore, an organic or inorganic film may be pre-applied to the substrate. For example, there may be an anti-reflective film or an underlayer of a multilayer resist, and a pattern may be formed on it. The substrate may also be pre-cleaned. For example, it can be cleaned using ultrapure water, acetone, or alcohol (methanol, ethanol, isopropyl alcohol).

[0116] As a method for applying the photosensitive resin composition of this disclosure to a substrate, known methods such as spin coating can be used.

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

[0118] The exposure dose for high-energy radiation is 1 mJ / cm². 2 More than 200mJ / cm 2 The following is preferable: 10 mJ / cm 2 More than 100mJ / cm 2 The following is more preferable:

[0119] (3)Developing process Next, the fluororesin film after the exposure process is developed with an alkaline aqueous solution to form a fluororesin pattern film. In other words, a fluororesin pattern film is formed by dissolving either the exposed or unexposed portion of the fluororesin film in an alkaline aqueous solution.

[0120] As the alkaline aqueous solution, aqueous solutions of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc., can be used. When the alkaline aqueous solution is an aqueous solution of tetramethylammonium hydroxide (TMAH), its concentration is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 2% by mass or more and 3% by mass or less.

[0121] The development method can be any known method, such as the dip method, paddle method, or spray method.

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

[0123] After development, a step may be provided to wash the fluororesin pattern film using deionized water or the like, if necessary. The washing method and washing time are preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0124] The bulkheads manufactured in this way can be used as display banks.

[0125] The display of the present disclosure is characterized by including a light-emitting element comprising a partition made of the photosensitive resin composition of the present disclosure and a light-emitting layer disposed in a region partitioned by the partition. Examples of displays include organic EL displays and quantum dot displays. [Examples]

[0126] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0127] 1. Synthesis of monomers [Synthesis Example 1] Synthesis of 5,5,5-trifluoro-2-methyl-1-penten-3-yne (TFMPY) 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 to a 500 mL glass flask equipped with a stirrer, and the mixture was cooled to -78°C. 100 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, followed by stirring for 30 minutes, and 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 three times with 100 mL of water, and then the fraction at 99 - 103°C was recovered by atmospheric distillation to obtain 5,5,5-trifluoro-2-methyl-3-pentyn-2-ol (hereinafter referred to as TFMPO) in a yield of 69% (10.5 g).

[0128]

Chemical formula

[0129]

Chemical formula

[0130] [NMR analysis results] 1 1H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.92 (1H, m) 5.52 (1H, m), 5.85 (1H, m) 19 19F-NMR (solvent: deuterated chloroform, reference substance: C6D6); δ (ppm) -49.8 (3F, s)

[0131] [Synthesis example 2] Synthesis of 4-hydroxystyrene (p-HO-St) (This was synthesized based on the examples described in Japanese Patent Publication No. 2016-98181.) In a 1000 ml glass flask equipped with a stirrer, 100 g of 4-acetoxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St) and 300 g of methanol were mixed at room temperature (approximately 20°C). 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, this 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 gradually added dropwise over 40 minutes, after which the mixture was stirred at 0°C for 30 minutes. 1 Analysis by 1H-NMR revealed no residual starting material. Next, an 18% by mass aqueous hydrochloric acid solution (equivalent to 0.8 equivalents of p-AcO-St) was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes after the completion of the addition. The pH of this solution was measured and found to be 6. The resulting reaction solution was extracted with 360 g of methyl-t-butyl ether at room temperature (approximately 20°C). The mixture was then washed twice with 330 g of purified water. 1,3,5-trihydroxybenzene was added to the resulting organic layer to an amount equivalent to 1% by mass of 4-hydroxystyrene. Subsequently, the 4-hydroxystyrene was 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 precipitate 4-hydroxystyrene crystals. The crystals were filtered off and further washed with n-octane. Next, the crystals were dried under reduced pressure at 25°C to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield 66%).

[0132] [ka]

[0133] 2. Manufacturing of fluororesin (First step: polymerization) [Measurement of the molar ratio of monomers constituting each repeating unit] NMR The molar ratio of monomers constituting each repeating unit in a polymer is: 1 H-NMR, 19 F-NMR or13 It was determined from the measurement values of 13C-NMR.

[0134] [Measurement of Polymer Molecular Weight] GPC The weight-average molecular weight Mw and the molecular weight distribution (the ratio of the number-average molecular weight Mn to the weight-average molecular weight Mw; Mw / Mn) of the polymer were measured using high-performance gel permeation chromatography (hereinafter sometimes referred to as GPC; manufactured by Tosoh Corporation, model HLC-8320GPC), connecting one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) in series, and using tetrahydrofuran (THF) as the eluent. A differential refractive index detector was used as the detector.

[0135] 2-1. Polymerization of Fluorine-containing Resin Precursor [Synthesis of Fluorine-containing Resin Precursor 1] In a 500 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 10.6 g (0.2 mol) of acrylonitrile (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AN), 49.8 g (0.15 mol) of 2-(perfluorobutyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C4F), 19.5 g (0.15 mol) of 2-hydroxyethyl methacrylate (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 taken, 1.6 g (0.01 mol) of 2,2'-azobis(2-methylbutyronitrile) (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and heated to an internal temperature of 75 °C and reacted for 6 hours. When 400 g of n-heptane was dropped into the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. Vacuum drying was carried out at 60 °C to obtain 69 g of fluorine-containing resin precursor 1 as a transparent viscous substance with a yield of 86%.

[0136] [13C-NMR Measurement Results] The composition ratio of the repeating units of the fluorine-containing resin precursor 1, expressed in mol%, was monomer unit derived from AN: monomer unit derived from MA-C4F: monomer unit derived from HEMA = 41:28:31.

[0137]

Chemical formula

[0138] <GPC measurement results> Mw = 6,700, Mw / Mn = 1.3

[0139] [Synthesis of fluorine-containing resin precursor 2] A fluorine-containing resin precursor 2 containing the following repeating units was obtained in a yield of 85% by the same procedure as the synthesis of the fluorine-containing resin precursor 1, except that 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F) was used instead of MA-C4F.

[0140] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2, expressed in mol%, was monomer unit derived from MN: monomer unit derived from MA-C6F: monomer unit derived from HEMA = 42:27:31.

[0141]

Chemical formula

[0142] <GPC measurement results> Mw = 6,300, Mw / Mn = 1.3

[0143] [Synthesis of fluorine-containing resin precursor 3] A fluorine-containing resin precursor 3 containing the following repeating units was obtained in a yield of 83% by the same procedure as the synthesis of the fluorine-containing resin precursor 1, except that methacrylonitrile (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MN) was used instead of AN.

[0144] <NMR measurement results> The composition ratio of each repeating unit of the fluororesin precursor 3 was, expressed in mol%, monomer unit derived from MN: monomer unit derived from MA-C4F: monomer unit derived from HEMA = 40:28:32.

[0145] [Chemical formula]

[0146] [GPC measurement results] Mw = 4,700, Mw / Mn = 1.3

[0147] [Synthesis of fluororesin precursor 4] A fluororesin precursor 4 containing the following repeating units was obtained in a yield of 83% by the same procedure as the synthesis of the fluororesin precursor 2, except that MN was used instead of AN.

[0148] [NMR measurement results] The composition ratio of each repeating unit of the fluororesin precursor 4 was, expressed in mol%, monomer unit derived from MN: monomer unit derived from MA-C6F: monomer unit derived from HEMA = 39:29:32.

[0149] [Chemical formula]

[0150] [GPC measurement results] Mw = 4,200, Mw / Mn = 1.3

[0151] [Synthesis of fluororesin precursor 5] A fluororesin precursor 5 containing the following repeating units was obtained in a yield of 80% by the same procedure as the synthesis of the fluororesin precursor 3-1, except that TFMPY obtained in Synthesis Example 1 was used instead of AN.

[0152] [NMR measurement results] The composition ratio of each repeating unit of the fluorine-containing resin precursor 5, expressed in mol%, was monomer unit derived from TFMPY: monomer unit derived from MA-C4F: monomer unit derived from HEMA = 38:30:32.

[0153] [Chemical formula]

[0154] [GPC measurement results] Mw = 4,400, Mw / Mn = 1.3

[0155] [Synthesis of fluorine-containing resin precursor 6] A fluorine-containing resin precursor 6 containing the following repeating units was obtained in a yield of 81% by the same procedure as the synthesis of the fluorine-containing resin precursor 2, except that TFMPY obtained in Synthesis Example 1 was used instead of AN.

[0156] [NMR measurement results] The composition ratio of each repeating unit of the fluorine-containing resin precursor 6, expressed in mol%, was monomer unit derived from TFMPY: monomer unit derived from MA-C6F: monomer unit derived from HEMA = 39:29:32.

[0157] [Chemical formula]

[0158] [GPC measurement results] Mw = 4,600, Mw / Mn = 1.3

[0159] [Synthesis of fluorine-containing resin precursor 7] In a 500 ml glass flask equipped with a stirrer at room temperature (about 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 taken, 1.6 g (0.01 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 75 °C and reacted for 6 hours. When 450 g of n-heptane was dropped into the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. Vacuum drying was carried out at 60 °C to obtain 74 g of a fluorine-containing resin precursor 7 as a transparent viscous substance with a yield of 84%.

[0160] <NMR measurement results> The composition ratio of the repeating units of the fluorine-containing resin precursor 7, expressed in mol%, was monomer unit derived from AN: monomer unit derived from MA-C4F: monomer unit derived from HEMA: monomer unit derived from MAA = 33:24:26:17.

[0161]

Chemical formula

[0162] <GPC measurement results> Mw = 7,700, Mw / Mn = 1.4

[0163] [Synthesis of fluorine-containing resin precursor 8] A fluorine-containing resin precursor 8 containing the following repeating units was obtained with a yield of 81% by the same procedure as the synthesis of the fluorine-containing resin precursor 7, except that MN was used instead of AN and MA-C6F was used instead of MA-C4F.

[0164] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 8, expressed in mol%, was 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.

[0165] [Chemical formula]

[0166] [GPC measurement result] Mw = 5,300, Mw / Mn = 1.3

[0167] [Synthesis of fluororesin precursor 9] A fluororesin precursor 9 containing the following repeating units was obtained in a yield of 81% by the same procedure as the synthesis of 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.

[0168] [NMR measurement result] The composition ratio of each repeating unit of the fluororesin precursor 9, expressed in mol%, was monomer unit derived from AN: monomer unit derived from MA-C6F: monomer unit derived from HEMA: monomer unit derived from AA = 34:23:27:16.

[0169] [Chemical formula]

[0170] [GPC measurement result] Mw = 6,900, Mw / Mn = 1.3

[0171] [Synthesis of fluororesin precursor 10] A fluororesin precursor 10 containing the following repeating units was obtained in a yield of 82% by the same procedure as the synthesis of fluororesin precursor 7, except that MN was used instead of AN and AA was used instead of MAA.

[0172] [NMR measurement result] The composition ratio of each repeating unit of the fluororesin precursor 10, expressed in mol%, was monomer unit derived from MN: monomer unit derived from MA-C4F: monomer unit derived from HEMA: monomer unit derived from AA = 33:24:26:17.

[0173] [Chemical formula]

[0174] <GPC measurement result> Mw = 5,500, Mw / Mn = 1.3

[0175] 2 - 2. Comparison of synthesis of fluorine-containing resin precursor [Comparative polymerization example 1] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of hexafluoroisopropyl methacrylate (manufactured by Central Glass Co., Ltd., hereinafter referred to as HFIP-M), 17.32 g (0.2 mol) of MAA, and 84 g of MEK were taken, 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and heated to 80 °C and then reacted for 6 hours. When the reaction solution after the reaction was dropped into 500 g of n-heptane, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at a temperature of 60 °C to obtain 55 g of comparative fluorine-containing resin precursor 1 as a white solid with a yield of 64%.

[0176] <NMR measurement result> The composition ratio of each repeating unit of comparative fluorine-containing resin precursor 1, expressed in molar ratio, was monomer unit derived from MA-C6F: monomer unit derived from HFIP-M: monomer unit derived from MAA = 26:20:54.

[0177] [Chemical formula]

[0178] <GPC measurement result> Mw = 9,700, Mw / Mn = 1.5

[0179] [Comparative polymerization example 2] In a 300 ml glass flask equipped with a stirrer, at room temperature, 13.01 g (0.1 mol) of HEMA, 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of HFIP-M, 8.66 g (0.1 mol) of MAA, and 88 g of MEK were taken. 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas. After heating to 80 °C, the reaction was carried out for 6 hours. When the reaction solution after the reaction was dropped into 500 g of n-heptane, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 60 g of a comparative fluorine-containing resin precursor 2 as a white solid, with a yield of 68%.

[0180] <NMR measurement results> The composition ratio of each repeating unit of the comparative fluorine-containing resin precursor 2, expressed in mol ratio, was monomer unit derived from HEMA: monomer unit derived from MA-C6F: monomer unit derived from HFIP-M: monomer unit derived from MAA = 24:26:24:26.

[0181]

Chemical formula

[0182] <GPC measurement results> Mw = 10,700, Mw / Mn = 1.5

[0183] [Comparative polymerization example 3] In a 300 ml glass flask equipped with a stirrer, 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 (product of Tokyo Chemical Industry Co., Ltd. Hereinafter referred to as HEVE), and 64 g of MEK were taken. 1.6 g (0.010 mol) of AIBN was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas. After heating to 80 °C, the reaction was carried out for 6 hours. When the reaction solution after the reaction was dropped into 500 g of n-heptane, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 °C to obtain 51 g of a comparative fluorine-containing resin precursor 3 as a white solid, with a yield of 81%.

[0184] <NMR measurement results> The composition ratio of each repeating unit of Comparative Fluorine-containing Resin Precursor 3, expressed in molar ratio, was Monomer unit derived from HEVE:Monomer unit derived from MA-C6F:Monomer unit derived from p-HO-St = 35:31:34.

[0185]

Chemical formula

[0186] <GPC measurement results> Mw = 17,300, Mw / Mn = 1.7

[0187] 3. Production of Fluorine-containing Resin (Second Step: Addition Reaction) Fluorine-containing resins were synthesized by reacting Fluorine-containing Resin Precursors 1 to 6 and Comparative Fluorine-containing Resin Precursors 1 to 3 obtained in "2. Production of Fluorine-containing Resin (First Step: Polymerization)" with an acrylic acid derivative. As the acrylic acid derivative, Karenz-AOI (manufactured by Showa Denko K.K.) was used. This reaction is an addition reaction between the hydroxyl group in each fluorine-containing resin precursor and the acrylic acid derivative.

[0188]

Chemical formula

[0189] [Synthesis of Fluorine-containing Resin 1] Into a 300 ml glass flask equipped with a stirrer, 10 g of Fluorine-containing Resin Precursor 1 (hydroxyl group equivalent 0.019 mol) and 20 g of PGMEA were taken, and 2.68 g (0.019 mol) of Karenz-AOI was added, followed by reaction at 45°C for 4 hours. After the reaction solution after the completion of the reaction was concentrated, 150 g of n-heptane was added to precipitate a solid. This precipitate was filtered off and dried under reduced pressure at 40°C to obtain 11.4 g of Fluorine-containing Resin 1 as a white solid with a yield of 90%.

[0190] < 13 <C-NMR measurement results> In fluororesin 1, the amount of acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) derived from KARENZ - AOI were 96:4 in terms of molar ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from AN, monomer unit derived from MA - C4F) that do not react with the crosslinking group site did not change from the fluororesin precursor 1 used (the same as before crosslinking group introduction).

[0191] [Synthesis of fluororesin 2] Fluororesin 2 was obtained at a yield of 91% by the same procedure as the synthesis of fluororesin 1, except that fluororesin precursor 2 was used instead of fluororesin precursor 1.

[0192] < 13 [C - NMR measurement results] In fluororesin 2, the amount of acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) derived from KARENZ - AOI were 95:5 in terms of molar ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from AN, monomer unit derived from MA - C6F) that do not react with the crosslinking group site did not change from the fluororesin precursor 2 used (the same as before crosslinking group introduction).

[0193] [Synthesis of fluororesin 3] Fluororesin 3 was obtained at a yield of 90% by the same procedure as the synthesis of fluororesin 1, except that fluororesin precursor 3 was used instead of fluororesin precursor 1.

[0194] < 13 [C - NMR measurement results] In fluororesin 3, the amount of acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) derived from KARENZ - AOI were 97:3 in terms of molar ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from MN, monomer unit derived from MA - C4F) that do not react with the crosslinking group site did not change from the fluororesin precursor 3 used (the same as before crosslinking group introduction).

[0195] [Synthesis of fluororesin 4] Except for using fluororesin precursor 4 instead of fluororesin precursor 1, fluororesin 4 was obtained in 89% yield using the same procedure as for the synthesis of fluororesin 1.

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

[0197] [Synthesis of Fluorine-containing Resin 5] Except for using fluororesin precursor 5 instead of fluororesin precursor 1, fluororesin 5 was obtained in a yield of 92% using the same procedure as for the synthesis of fluororesin 1.

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

[0199] [Synthesis of fluororesin 6] Except for using fluororesin precursor 6 instead of fluororesin precursor 1, fluororesin 6 was obtained in 89% yield using the same procedure as for the synthesis of fluororesin 1.

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

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

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

[0203] [Synthesis of Fluorine-containing Resin 8] Except for using fluororesin precursor 8 instead of fluororesin precursor 7, fluororesin 8 was obtained in a yield of 93% using the same procedure as for the synthesis of fluororesin 7.

[0204] < 13 C-NMR measurement results> In the fluororesin 8, the introduced amount (reaction rate) of the acrylic acid derivative derived from KARENZ-AOI and the amount of residual alcoholic hydroxyl groups (unreacted rate) were 97:3 in terms of mol ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C6F) that does not react with the crosslinking group site did not change from the used fluororesin precursor 8 (the same as before the introduction of the crosslinking group).

[0205] [Synthesis of fluororesin 9] Fluororesin 9 was obtained in a yield of 90% by the same procedure as the synthesis of fluororesin 7, except that fluororesin precursor 9 was used instead of fluororesin precursor 7.

[0206] < 13 C-NMR measurement results In the fluororesin 9, the introduced amount (reaction rate) of the acrylic acid derivative derived from KARENZ-AOI and the amount of residual hydroxyl groups (unreacted rate) were 95:5 in terms of mol ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from AN, monomer unit derived from MA-C6F) that does not react with the crosslinking group site did not change from the used fluororesin precursor 9 (the same as before the introduction of the crosslinking group).

[0207] [Synthesis of fluororesin 10] Fluororesin 10 was obtained in a yield of 93% by the same procedure as the synthesis of fluororesin 7, except that fluororesin precursor 10 was used instead of fluororesin precursor 7.

[0208] < 13 C-NMR measurement results In the fluororesin 10, the introduced amount (reaction rate) of the acrylic acid derivative derived from KARENZ-AOI and the amount of residual hydroxyl groups (unreacted rate) were 96:4 in terms of mol ratio. Also, it was confirmed that the composition ratios of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C4F) that does not react with the crosslinking group site did not change from the used fluororesin precursor 10 (the same as before the introduction of the crosslinking group).

[0209] [Synthesis of comparative fluororesin 1] The comparative fluororesin 1 was obtained in 89% yield using the same procedure as for the synthesis of fluororesin 1, except that comparative fluororesin precursor 1 was used instead of fluororesin precursor 1.

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

[0211] [Synthesis of comparative fluororesin 2] The comparative fluororesin 2 was obtained in 90% yield using the same procedure as for the synthesis of fluororesin 1, except that comparative fluororesin precursor 2 was used instead of fluororesin precursor 1.

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

[0213] [Synthesis of comparative fluororesin 3] The comparative fluororesin 3 was obtained in 90% yield using the same procedure as for the synthesis of fluororesin 1, except that comparative fluororesin precursor 3 was used instead of fluororesin precursor 1.

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

[0215] 4. Preparation of photosensitive resin composition [Preparation of photosensitive resin composition 1] A photosensitive resin composition 1 was prepared by blending 0.5 parts by mass of the manufactured fluororesin 1, 0.5 parts by mass of Irgacure 369 (product of BASF Co., Ltd.) as a photopolymerization initiator, 50 parts by mass of pentaerythritol tetraacrylate (product of Tokyo Chemical Industry Co., Ltd.) as a crosslinking agent, 50 parts by mass of ZAR2051H (product of 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, and filtering the resulting solution through a 0.2 μm membrane filter.

[0216] [Preparation of photosensitive resin composition 2] Photosensitive resin composition 2 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 2 was used instead of fluororesin 1.

[0217] [Preparation of photosensitive resin composition 3] Photosensitive resin composition 3 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 3 was used instead of fluororesin 1.

[0218] [Preparation of photosensitive resin composition 4] Photosensitive resin composition 4 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 4 was used instead of fluororesin 1.

[0219] [Preparation of photosensitive resin composition 5] Photosensitive resin composition 5 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 5 was used instead of fluororesin 1.

[0220] [Preparation of photosensitive resin composition 6] Photosensitive resin composition 6 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 6 was used instead of fluororesin 1.

[0221] [Preparation of photosensitive resin composition 7] Photosensitive resin composition 7 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 7 was used instead of fluororesin 1.

[0222] [Preparation of photosensitive resin composition 8] Photosensitive resin composition 8 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 8 was used instead of fluororesin 1.

[0223] [Preparation of photosensitive resin composition 9] The photosensitive resin composition 9 was prepared using the same procedure as for the preparation of the photosensitive resin composition 1, except that the fluororesin 9 was used instead of the fluororesin 1.

[0224] [Preparation of photosensitive resin composition 10] Photosensitive resin composition 10 was prepared using the same procedure as for the preparation of photosensitive resin composition 1, except that fluororesin 10 was used instead of fluororesin 1.

[0225] [Preparation of comparative photosensitive resin composition 1] The comparative photosensitive resin composition 1 was prepared using the same procedure as for the preparation of the photosensitive resin composition 1, except that comparative fluororesin 1 was used instead of fluororesin 1.

[0226] [Preparation of comparative photosensitive resin composition 2] The comparative photosensitive resin composition 2 was prepared using the same procedure as for the preparation of the photosensitive resin composition 1, except that the comparative fluororesin 2 was used instead of the fluororesin 1.

[0227] [Preparation of comparative photosensitive resin composition 3] The comparative photosensitive resin composition 3 was prepared using the same procedure as for the preparation of the photosensitive resin composition 1, except that the comparative fluororesin 3 was used instead of the fluororesin 1.

[0228] 5. Bank's evaluation Using the photosensitive resin compositions 1-10 and comparative photosensitive resin compositions 1-3 obtained in "4. Preparation of Photosensitive Resin Compositions," banks 1-10 and comparative banks 1-3 were formed, and the bank performance was evaluated and compared. The results for the banks of this disclosure and the comparative banks are shown in Table 1.

[0229] [Bank formation] A 10cm square ITO substrate was washed with ultrapure water, then with acetone, and then UV ozone treatment was performed on the substrate for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Source Co., Ltd., model number: PL17-110). Next, using photosensitive resin compositions 1-10 and comparative photosensitive resin compositions 1-3 obtained in "4. Preparation of Photosensitive Resin Compositions," the resulting UV ozone-treated substrates were coated using a spin coater at a rotation speed of 1,000 rpm, and heated on a hot plate at 100°C for 150 seconds to form a fluororesin film and a comparative fluororesin film with a thickness of 2 μm. Using a mask aligner (manufactured by Suss Microtec Co., Ltd.), the obtained resin films were exposed by irradiating them with i-line light (wavelength 365 nm) through a mask with a line and space of 5 μm. The resulting resin film after exposure was evaluated for developer solubility, bank performance (sensitivity, resolution), and contact angle.

[0230] [Developer solubility] The resin film exposed on an ITO substrate was immersed in an alkaline developer for 80 seconds at room temperature to evaluate its solubility in the alkaline developer. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used as the alkaline developer. The solubility of the bank was evaluated by measuring the thickness of the bank after immersion using a contact-type film thickness gauge. "Soluble" was defined as complete dissolution of the bank, and "insoluble" was defined as remaining undissolved. The results are shown in Table 1.

[0231] [Bank performance (sensitivity, resolution)] The optimal exposure amount Eop(mJ / cm²) for forming the bank pattern described above, which is a line-and-space pattern. 2 The value of ) was determined and used as an indicator of sensitivity. Furthermore, the obtained bank patterns were observed under a microscope to evaluate their resolution. Patterns where no line edge roughness could be observed were rated "Excellent," those with slight roughness were rated "Good," and those with significant roughness were rated "Poor." The results are shown in Table 1.

[0232] [Table 1]

[0233] [Contact angle] The substrate having banks obtained by the above process was heated at 230°C for 60 minutes, and then the entire surface of the substrate was subjected to UV ozone treatment or oxygen plasma treatment for 10 minutes. After that, it was heated at 230°C for 60 seconds. The contact angles of each bank surface with respect to anisole, PGMEA, and water were measured using a contact angle meter (Kyowa Interface Science Co., Ltd., model number: DMs-601) before and after the UV ozone treatment or oxygen plasma treatment, and after the subsequent heating process. The results are shown in Table 2. The UV ozone treatment device used was the same one described above. Furthermore, the oxygen plasma treatment was performed using a Plasma Dry Cleaner PDC210 manufactured by Yamato Scientific Co., Ltd., under conditions of an oxygen gas flow rate of 30 cc / min and an output of 300 W.

[0234] [Table 2]

[0235] As shown in Table 1, both the bank of this disclosure and the comparative bank were negative-type resists in developer solubility evaluation, with only the unexposed areas dissolving. In bank performance evaluation, they showed similar sensitivity, with 5 μm lines and spaces of the mask being transferred with good resolution and no line edge roughness observed, resulting in a resolution rating of "excellent". In other words, these evaluations showed that the fluororesin of this disclosure and the comparative fluororesin had little effect on the bank.

[0236] On the other hand, as shown in Table 2, in the bank of this disclosure, the contact angles of the exposed area (corresponding to the upper surface of the bank) with respect to anisole, PGMEA, and water decreased with UV ozone treatment or oxygen plasma treatment, but increased with the subsequent heating process, showing good liquid repellency. In the comparative bank, the contact angle decreased with UV ozone treatment or oxygen plasma treatment, and remained low with almost no change even with the subsequent heating process.

Claims

1. A fluororesin characterized by containing repeating units (U) that include monomers (A) having triple bonds in their side chains as monomer units.

2. The fluorine-containing resin according to claim 1, wherein the fluorine atom content is 5% by mass or more.

3. The fluorine-containing resin according to claim 1 or 2, wherein at least some of the side chains of the monomer (A) contain fluorine atoms.

4. The fluororesin according to any one of claims 1 to 3, wherein at least a portion of the triple bond is a carbon-nitrogen triple bond of a nitrile group.

5. The fluororesin according to any one of claims 1 to 4, 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 alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O)-CH ３ . R ２ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cyclic alkyl group having 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group may be substituted with a fluorine atom.)

6. The fluororesin according to claim 5, wherein the structure represented by formula (1) or (1') is the 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 equations (2) and (2'), R １ represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups or -O-C(=O)-CH ３ It may be replaced with R. ｆ (This represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.)

7. The fluororesin according to any one of claims 1 to 6, wherein the repeating unit (U) includes the 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 equations (3) and (3'), R １ represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups or -O-C(=O)-CH ３ It may be replaced with R. ２ (This represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.)

8. The fluororesin according to claim 7, wherein the structure represented by formula (3) or formula (3') is the 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 equations (4) and (4'), R １ represents a hydrogen atom, a fluorine atom, or a methyl group. X represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups or -O-C(=O)-CH ３ It may be replaced with R. ｆ (This represents a linear perfluoroalkyl group with 1 to 6 carbon atoms, a branched perfluoroalkyl group with 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group with 3 to 6 carbon atoms.)

9. A liquid repellent characterized by containing a fluororesin according to any one of claims 1 to 8.

10. A photosensitive resin composition characterized by comprising at least a fluororesin according to any one of claims 1 to 8, a solvent, and a photopolymerization initiator.

11. Furthermore, the photosensitive resin composition according to claim 10 further comprises a crosslinking agent and an alkali-soluble resin.

12. A photosensitive resin composition according to claim 10 or 11, used for forming a partition wall.

13. A cured product characterized by being obtained by curing a photosensitive resin composition according to any one of claims 10 to 12.

14. A partition made of the cured material described in claim 13, A display characterized by including a light-emitting element, which comprises a light-emitting layer disposed in a region partitioned by the aforementioned partition wall.

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

Images