Surface modifiers, photosensitive resin compositions, cured products, and displays

Abstract

The purpose of the present disclosure is to provide a novel surface modifier which can improve the surface roughness of a fluorine-containing resin suitable for use as a partition wall material when introduced to a photosensitive resin composition. The present disclosure is a surface modifier containing a fluorine-containing resin (A) having a structure represented by general formula (1). (In general formula (1), Ra's each independently represent a C1-C6 linear, C3-C6 branched, or C3-C6 cyclic alkyl group, or a fluorine atom, and an arbitrary number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)

Description

[Technical Field]

[0001] This disclosure relates to surface modifiers, photosensitive resin compositions, cured products, and displays. [Background technology]

[0002] When manufacturing display elements such as organic EL displays, micro-LED displays, and quantum dot displays, the inkjet method is known as a method for forming organic layers that have functions such as light emission. There are several inkjet methods, and specifically, examples include a method in which ink is dropped from a nozzle into the recesses of a pattern film with irregularities formed on a substrate and solidified, or a method in which ink droplets are dropped onto a pattern film that has been pre-formed on a substrate with hydrophilic areas (areas that are wetted by ink) and liquid-repellent areas (areas that repel ink), and ink is deposited only on the hydrophilic areas.

[0003] In particular, in the method of solidifying ink dropped from a nozzle into the recesses of the patterned film mentioned above, two main methods can be employed to produce such a patterned film with these irregularities. One is photolithography, which involves exposing the surface of a photosensitive resist film coated on a substrate in a patterned manner to form exposed and unexposed areas, and then dissolving and removing either area with a developer. The other is imprint, which uses printing technology.

[0004] The raised portions of the formed pattern film are called banks (septaments), and when ink is dropped into the recesses of the pattern film, the banks act as barriers to prevent the inks from mixing. To enhance this barrier effect, the recesses of the pattern film are required to expose the substrate surface, which must be hydrophilic to the ink, while the upper surface of the banks must be liquid-repellent to the ink.

[0005] Fluorine-containing resins are used as ink-repellent agents to form 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 monomers represented by the following formula 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)COOXR f1 (In the formula, R represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and X represents a divalent organic group having 1 to 6 carbon atoms that does not contain a fluorine atom, R f1 This represents a perfluoroalkyl group with 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 monomers represented by the following formula, 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)COOXR f1 (wherein R and R f1 (The same applies as above.)

[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 fluorine atom content in the ink-repellent agent (E) is 1 to 40% by mass, and the ink-repellent agent (E) has an ethylenically active double bond. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Patent No. 4474991 [Patent Document 2] Patent No. 4488098 [Patent Document 3] Patent No. 4905563 [Patent Document 4] Patent No. 6536578 [Overview of the project] [Problems that the invention aims to solve]

[0011] The fluororesins and ink-repellent agents disclosed in Patent Documents 1 to 4 are resins with excellent liquid-repellent properties and are suitable as partition materials. On the other hand, it has been found that these resins still have room for improvement in terms of surface roughness after curing. This disclosure aims to improve the surface roughness of fluororesins suitable for use as partition materials. [Means for solving the problem]

[0012] 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 fluororesin having a specific group as a surface modifier, leading to this disclosure.

[0013] In other words, this disclosure is as follows: The surface modifier disclosed herein includes a fluororesin (A) having a structure represented by the following general formula (1).

[0014] [ka]

[0015] (In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.) By introducing the surface modifier of this disclosure into a photosensitive resin composition, a partition wall with improved surface roughness can be produced.

[0016] The photosensitive resin composition of this disclosure comprises the above-mentioned surface modifier, a fluororesin (B) having a crosslinked portion, a solvent, and a photopolymerization initiator. By using the photosensitive resin composition of this disclosure, partitions with improved surface roughness can be manufactured.

[0017] The cured product of this disclosure is characterized by being obtained by curing a photosensitive resin composition. By using the photosensitive resin composition of this disclosure, cured products and partitions with improved surface roughness can be produced.

[0018] The display of this disclosure includes a light-emitting element comprising a partition obtained by curing the above-mentioned photosensitive resin composition, and a light-emitting layer or wavelength conversion layer disposed in a region partitioned by the partition. The display of this disclosure includes a light-emitting element on which ink is patterned with high precision, by comprising a partition obtained from the above-mentioned photosensitive resin composition.

[0019] The surface treatment method for molded articles according to this disclosure uses a fluororesin (A) having the structure represented by the general formula (1) above.

[0020] The use of this disclosure is the use of a fluororesin (A) having the structure represented by the above general formula (1) for preparing the surface of a molded article. [Effects of the Invention]

[0021] According to this disclosure, the surface roughness of fluororesins suitable for use as partition materials can be improved. [Modes for carrying out the invention]

[0022] The present disclosure is described in detail below. This disclosure is not limited to the embodiments described below, and may be implemented as appropriate based on the ordinary knowledge of a person skilled in the art, without prejudice to the spirit of this disclosure. (Surface modifier) <Fluorine resin (A)> The surface modifier disclosed herein includes a fluororesin (A) having a structure represented by the following general formula (1).

[0023] [ka]

[0024] In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. Examples of linear alkyl groups having 1 to 6 carbon atoms include trifluoromethyl, difluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 3,3,3-trifluoropropyl, and nonafluorobutyl groups. Examples of branched alkyl groups having 3 to 6 carbon atoms include heptafluoroisopropyl, hexafluoroisopropyl, nonafluoroisobutyl, and nonafluoro-tert-butyl groups. Examples of cyclic alkyl groups having 3 to 6 carbon atoms include pentafluorocyclopropyl. Ra is preferably a linear alkyl group having 1 to 6 carbon atoms, and more preferably a trifluoromethyl group. Specific examples of the structure represented by general formula (1) include a difluoromethanol group, a tetrafluoroethanol group, a hexafluoroisopropanol group, a trifluoropropanol group, and so on, with the hexafluoroisopropanol group being preferred. In fluororesin (A), it is preferable that the structure represented by general formula (1) is not directly bonded to the aromatic ring. It is preferable that the structure represented by general formula (1) is directly bonded to a linear, branched, or cyclic alkylene group.

[0025] Fluorine-containing resin (A) can be obtained by polymerizing monomers having a structure represented by general formula (1). Examples of monomers having the structure represented by general formula (1) include 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl methacrylate, 4-(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)styrene(4-HFA-ST), 3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)styrene(3,5-HFA-ST), and 2,4-bis(1,1,1,3,3,3-hexafluoro Examples include oro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, 3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, 2,4,6-tris(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, and 1,3-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)isopropyl methacrylate. These monomers can be used individually or in combination of two or more. Preferably, the methacrylates are 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl, 3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, or 1,3-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)isopropyl methacrylate. In one embodiment, the fluororesin (A) is preferably a homopolymer obtained by polymerizing only one of these monomers, or a heteropolymer obtained by copolymerizing any two or more of these monomers. This is because polymerization is easy and it also has excellent performance as a surface modifier.

[0026] The fluororesin (A) may contain constituent units derived from monomers other than the monomer having the structure represented by general formula (1). Examples of such other monomers include monomers used in the synthesis of the fluororesin (B) having the crosslinking site described later. One or more of these other monomers may be used. Specific examples of these other monomers include hexafluoroisopropyl methacrylate and butyl methacrylate.

[0027] If the fluororesin (A) contains constituent units derived from the other monomers mentioned above, the content of these units is preferably 50 mol% or less of the fluororesin (A). If the constituent units derived from the other monomers exceed 50 mol%, the surface conditioning effect of the fluororesin (A) may not be sufficiently obtained. More preferably, it is 30 mol% or less. The molar ratio of constituent units derived from each monomer in fluororesin (A) can be determined from NMR (nuclear magnetic resonance spectroscopy) measurements. In this disclosure, since the fluororesin (A) functions as a surface modifier, it is preferable that it does not have crosslinking sites.

[0028] The fluororesin (A) preferably contains a structure represented by general formula (1) in an amount of 50 mol% or more and 300 mol% or less, with the total amount of repeating units constituting the fluororesin (A) being 100 mol%. If the content of the structure represented by general formula (1) is less than 50 mol%, the effect of the fluororesin (A) as a surface modifier may not be sufficiently obtained. If it exceeds 300 mol%, it is undesirable because the synthesis process is time-consuming and the manufacturing cost is high. More preferably, it is 100 mol% or more and 200 mol% or less.

[0029] The fluororesin (A) preferably has a weight-average molecular weight of 1,000 or more and 50,000 or less. If the weight-average molecular weight of the fluororesin (A) is outside the above range, the surface roughness of the resin film and partition may not be sufficiently improved. More preferably, it is 5,000 or more and 40,000 or less, and even more preferably 5,000 or more and 30,000 or less. The degree of dispersion of the fluororesin (A) (ratio of weight-average molecular weight Mw to number-average molecular weight Mn; Mw / Mn) is preferably 1.01 to 5.00, more preferably 1.10 to 4.00, and particularly preferably 1.30 to 3.00. In this disclosure, the weight-average molecular weight and dispersion of the fluororesin (A) are values ​​obtained by high-speed gel permeation chromatography using polystyrene as the standard substance.

[0030] Fluorine-containing resin (A) can be synthesized, for example, by dissolving a monomer in a solvent, adding a polymerization initiator, and heating as needed to cause a reaction. In this reaction, it is preferable to include a chain transfer agent as needed. The monomer, solvent, polymerization initiator, and chain transfer agent may be added all at the start of the reaction or added continuously.

[0031] The solvent used in the above synthesis method is not particularly limited and can include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, fluorinated solvents, etc. These may be used individually or in combination of two or more.

[0032] Examples of ketones include acetone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptylcyclopentanone, 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-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, oleyl alcohol, and the like.

[0033] 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), and monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0034] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole. 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.

[0035] Examples of fluorinated solvents include chlorofluorocarbons (CFCs), alternative CFCs, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0036] Examples of polymerization initiators include well-known organic peroxides, inorganic peroxides, and azo compounds. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with reducing agents.

[0037] Examples of chain transfer agents include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol; and alkyl halides such as chloroform, carbon tetrachloride, and carbon tetrabromide.

[0038] The content of the fluororesin (A) in the surface modifier of this disclosure is not particularly limited, but is preferably 0.001 to 99.99% by mass, and more preferably 0.01 to 99.9% by mass. The fluororesin (A) in the surface modifier of this disclosure may be a single type or a mixture of two or more types. The surface modifier of this disclosure may contain solvents and additives other than the fluororesin (A). Examples of solvents that may be contained in the surface modifier of this disclosure include PGMEA and butyl acetate.

[0039] The surface modifier of the present disclosure can be suitably used as a surface modifier for various resins by containing a fluororesin (A) having a structure represented by general formula (1). For example, by introducing the surface modifier of the present disclosure into a resin composition, molded articles such as resin films and partitions (banks) with improved surface roughness can be produced. The type of resin in the resin composition is not particularly limited, and examples include one or more types of olefin resins, epoxy resins, (meth)acrylic resins, urethane resins, fluororesins, etc. The surface modifier of the present disclosure can be particularly suitably used in compositions containing two or more resins with different fluorine content. The surface modifiers disclosed herein can be used more specifically as defoaming agents, leveling agents, anti-wrinkle agents, etc. Furthermore, since the surface modifiers disclosed herein also have surfactant properties, they can also be used as surfactants.

[0040] (Photosensitive resin composition) The photosensitive resin composition of this disclosure comprises the above-mentioned surface modifier, a fluororesin (B) having crosslinked portions, a solvent, and a photopolymerization initiator. By using the photosensitive resin composition containing the above-mentioned surface modifier, resin films and partitions with improved surface roughness can be produced. 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. Examples of surface modifiers in the photosensitive resin composition of this disclosure include those containing the fluororesin (A) described above. In the photosensitive resin composition of this disclosure, the content of the fluororesin (A) is preferably 0.01% by mass or more and 4.0% by mass or less based on the total solid content of the photosensitive resin composition. If it is outside the above range, the surface roughness of the resin film and partition may not be sufficiently improved. More preferably, it is 0.1% by mass or more and 2.5% by mass or less, and even more preferably 0.2% by mass or more and 2.5% by mass or less.

[0041] <Fluorine-containing resin (B) having cross-linked regions> In the photosensitive resin composition of this disclosure, the fluororesin (B) having a crosslinked site has repeating units made of hydrocarbons having fluorine atoms, and the side chains of the polymer have photopolymerizable groups as crosslinked sites. In this disclosure, the crosslinked site of "fluororesin (B) having a crosslinked site" means a site that can polymerize with other monomers. In the following, "fluororesin containing crosslinked portions (B)" will also be referred to as "fluororesin (B)".

[0042] In the photosensitive resin composition of this disclosure, the fluororesin (B) may have a structure represented by the following chemical formula (2), or it may have a structure represented by the following formula (3).

[0043] [ka] (In formula (2), each Rb independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. R 2 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms.)

[0044] [Chemical formula] (In formula (3), each Rb independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. R 1 represents a hydrogen atom, a fluorine atom or a methyl group. R 2 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms.)

[0045] In formula (3), R 1 is preferably a hydrogen atom or a methyl group. Also, examples of R 2 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, an n-hexyl group, a cyclopentyl group, a cyclohexyl group, etc. A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group are preferred, and a hydrogen atom and a methyl group are more preferred.) Furthermore, Rb in formula (2) or formula (3) is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, an n-nonafluorobutyl group, an isononafluorobutyl group, or a tert-nonafluorobutyl group; more preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, or a hexafluoroisopropyl group; and particularly preferably a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

[0046] The following structures are examples of preferred repeating units represented by formula (3) in the fluororesin (B) of the photosensitive resin composition of this disclosure.

[0047] [ka]

[0048] [ka]

[0049] The content of the repeating units represented by formula (3) in the fluororesin (B) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 10 mol% to 30 mol%, based on 100 mol% of the total repeating units constituting the fluororesin (B).

[0050] When the content of the repeating units of formula (3) exceeds 70 mol%, the fluororesin (B) tends to become less soluble in the solvent. On the other hand, when the content of the repeating units of formula (3) is less than 5 mol%, the resistance tends to decrease when subjected to UV ozone treatment or oxygen plasma treatment.

[0051] A fluororesin (B) having repeating units represented by formula (3) is one preferred embodiment because it has resistance to UV ozone treatment or oxygen plasma treatment.

[0052] Furthermore, in the photosensitive resin composition of this disclosure, the fluororesin (B) may include a structure represented by the following formula (4).

[0053] [ka]

[0054] In equation (4), R 3 , R 4 Each of these independently represents either a hydrogen atom or a methyl group.

[0055] In equation (4), W 1 The symbol represents a divalent linking group, and can be -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH- are preferred.

[0056] W 1 However, when it is -OC(=O)-NH-, it exhibits superior liquid repellency against ink after UV ozone treatment or oxygen plasma treatment, making it one of the preferred embodiments.

[0057] In equation (4), A 1 represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3.

[0058] Divalent linking group A 1When it refers to a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0059] Divalent linking group A 1 When this refers to a branched alkylene group having 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene groups.

[0060] Divalent linking group A 1 When it is a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0061] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include hydroxyethylene, 1-hydroxy-n-propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene, 2-hydroxy-n-butylene, hydroxy-sec-butylene (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene (-C(CH2OH)(CH3)CH2-).

[0062] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, an example of such a substituted alkylene group is one in which the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is replaced with -OC(=O)-CH3.

[0063] In particular, divalent linking group A 1 The group is preferably a methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 2-hydroxy-n-butylene group, or hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), more preferably an ethylene group, propylene group, 2-hydroxy-n-propylene group, or hydroxy-isopropylene group (-CH(CH2OH)CH2-), and particularly preferably an ethylene group or a 2-hydroxy-n-propylene group.

[0064] In equation (4), Y 1 represents a divalent linking group, which represents -O- or -NH-, and is more preferably -O-.

[0065] In equation (4), n represents an integer between 1 and 3, and it is particularly preferable that n is 1. The substitution positions of the aromatic ring independently represent the ortho, meta, and para positions, with the para position being preferable.

[0066] Regarding the repeating unit represented by formula (4), the following structures are examples of preferred structures. While the example shows the substitution position of the aromatic ring at the para position, the substitution positions may independently be at the ortho and meta positions.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] The content of the repeating units represented by formula (4) in the fluororesin (B) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 10 mol% to 30 mol%, based on 100 mol% of the total repeating units constituting the fluororesin (B).

[0072] When the content of the repeating units of formula (4) exceeds 70 mol%, the fluororesin (B) tends to become less soluble in the solvent. On the other hand, when the content of the repeating units of formula (4) is less than 5 mol%, the resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

[0073] While the effects of the repeating unit represented by formula (4) in this disclosure are not entirely clear, it is presumed that it possesses resistance to UV ozone treatment or oxygen plasma treatment. However, the effects of this disclosure are not limited to those described herein.

[0074] As described above, the fluororesin (B) of this disclosure may be a mixture (blend) of a copolymer containing repeating units represented by formula (3) and repeating units represented by formula (4) and another type of copolymer containing repeating units represented by formula (3) and repeating units represented by formula (4). In particular, the fluororesin (B) of this disclosure may be a mixture of W in formula (4). 1 A fluororesin containing repeating units of -OC(=O)-NH- and W in formula (4) 1 One preferred embodiment of this disclosure is that the mixture is with a fluororesin containing repeating units of -C(=O)-NH-.

[0075] Furthermore, in the photosensitive resin composition of this disclosure, the fluororesin (B) may include a structure represented by the following formula (5).

[0076] [ka]

[0077] In equation (5), R 5 , R 6 Each of these independently represents either a hydrogen atom or a methyl group.

[0078] In equation (5), W 2 The symbol represents a divalent linking group, and can be -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH- are preferred.

[0079] W 2 However, when the compound is -OC(=O)-NH-, the liquid repellency of the fluororesin (B) of this disclosure to ink after UV ozone treatment or oxygen plasma treatment is superior, making this a particularly preferred embodiment.

[0080] In equation (5), A 2 , A 3 Each of these independently represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3.

[0081] Divalent linking group A 2 , A 3 When each of these is independently a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0082] Divalent linking group A 2 , A 3Each of these can be an independent branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, isohexalene, etc.

[0083] Divalent linking group A 2 , A 3 When each of these is independently a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0084] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene group (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene group (-C(CH2OH)(CH3)CH2-).

[0085] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, an example of such a substituted alkylene group is one in which the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is replaced with -OC(=O)-CH3.

[0086] In particular, divalent linking group A 2 , A 3These are, independently, a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH2-), a 2-hydroxyethylene group (-CH2CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH2OH)CH2-), a 2-hydroxy-n-butylene group, and a hydroxy-sec-butylene group (-CH(CH 2OH)CH2CH2- is preferred, ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-) is more preferred, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH2-), and 2-hydroxyethylene group (-CH2CH(OH)-) are particularly preferred.

[0087] In equation (5), Y 2 , Y 3 The '' represents a divalent linking group, which independently represents -O- or -NH-, with -O- being more preferable.

[0088] In equation (5), n represents an integer between 1 and 3, and it is particularly preferable that n is 1.

[0089] In equation (5), r represents either 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0090] The following structures are examples of preferred repeating units represented by equation (5).

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] The content of the repeating units represented by formula (5) in the fluororesin (B) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 10 mol% to 30 mol%, based on 100 mol% of the total repeating units constituting the fluororesin (B).

[0097] If the content of the repeating units of formula (5) is greater than 70 mol%, the fluororesin (B) tends to become less soluble in the solvent. On the other hand, if the content of the repeating units of formula (5) is less than 5 mol%, the adhesion of the resin film or bank obtained from the fluororesin (B) to the substrate tends to decrease.

[0098] Although the effects of the repeating units represented by formula (5) are not clear, it is presumed that the inclusion of the repeating units represented by formula (5) in the fluororesin (B) improves the adhesion of the resulting resin film or bank to the substrate. However, the effects of this disclosure are not limited to those described herein.

[0099] The fluororesin (B) may be a mixture (blend) of a copolymer containing repeating units represented by formula (3) and repeating units represented by formula (5), and another type of copolymer containing repeating units represented by formula (3) and repeating units represented by formula (5). In particular, the fluororesin of this disclosure is W in formula (5). 2 A fluororesin containing repeating units of -OC(=O)-NH- and W in formula (5) 2One preferred embodiment of this disclosure is that the mixture is with a fluororesin containing repeating units of -C(=O)-NH-.

[0100] Furthermore, in the photosensitive resin composition of this disclosure, the fluororesin (B) may include a structure represented by the following formula (6).

[0101] [ka]

[0102] In formula (6), R 7 represents a hydrogen atom or a methyl group.

[0103] In formula (6), R 8 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, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the fluorine content in the repeating unit is 30% by mass or more.

[0104] R 8 When is a linear alkyl group, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or any number of hydrogen atoms of a linear alkyl group having 10 to 14 carbon atoms substituted with fluorine atoms.

[0105] R 8 When is a linear alkyl group, the repeating unit represented by formula (6) above is preferably the repeating unit represented by formula (6-1) below.

[0106] [ka]

[0107] In formula (6-1), R 9 R in equation (6) 7 It is synonymous with [the above].

[0108] In equation (6-1), X is either a hydrogen atom or a fluorine atom.

[0109] In equation (6-1), p is an integer between 1 and 4. q is an integer between 1 and 14. It is particularly preferable that p is an integer between 1 and 2, q is an integer between 2 and 8, and X is a fluorine atom.

[0110] The following structures are examples of preferred repeating units represented by equation (6).

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] The content of the repeating units represented by formula (6) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 10 mol% to 30 mol%, based on 100 mol% of the total repeating units constituting the fluororesin (B).

[0116] When the content of the repeating units in formula (6) exceeds 70 mol%, the fluororesin (B) tends to become less soluble in the solvent.

[0117] The repeating unit represented by formula (6) is a repeating unit that provides liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. Therefore, if high liquid repellency to ink is desired, it is preferable to include the repeating unit represented by formula (6) in the fluororesin (B) of this disclosure.

[0118] Furthermore, in the photosensitive resin composition of this disclosure, the fluororesin (B) may include a structure represented by the following formula (7).

[0119] [ka]

[0120] In formula (7), R 10 represents a hydrogen atom or a methyl group.

[0121] In formula (7), B is independently a hydroxyl group, a carboxyl group, and -C(=O)-OR 11 (R 11 R 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, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. 11 (The fluorine content inside is 30% by mass or more) or -OC(=O)-R 12 (R 12 represents a linear alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms. m represents an integer between 0 and 3.

[0122] The following structures are examples of preferred repeating units represented by equation (7).

[0123] [ka]

[0124] [ka]

[0125] The content of the repeating units represented by formula (7) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and particularly preferably 20 mol% to 40 mol%, based on 100 mol% of the total repeating units constituting the fluororesin (B).

[0126] When the content of the repeating units in formula (7) exceeds 70 mol%, the fluororesin (B) tends to become less soluble in the solvent.

[0127] In formula (7), when B is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (7) is soluble in alkaline developing solutions. Therefore, if it is desired to impart alkali developability to a fluororesin film obtained from the fluororesin (B), it is preferable that the fluororesin (B) of this disclosure contains the repeating unit represented by formula (7) when B is a hydroxyl group or a carboxyl group.

[0128] Furthermore, in the photosensitive resin composition of this disclosure, the fluororesin (B) may include a structure represented by the following formula (8).

[0129] [ka]

[0130] In equation (8), R 13 represents a hydrogen atom or a methyl group.

[0131] In equation (8), A 4 represents a divalent linking group, and represents a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH3.

[0132] Divalent linking group A 4When it refers to a linear alkylene group having 1 to 10 carbon atoms, examples include the methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexalene group, n-heptalene group, n-octalene group, n-nonalene group, and n-decalene group.

[0133] Divalent linking group A 4 When this refers to a branched alkylene group having 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene groups.

[0134] Divalent linking group A 4 When it is a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0135] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)CH2CH2-), hydroxy-isobutylene group (-CH2CH(CH2OH)CH2-), and hydroxy-tert-butylene group (-C(CH2OH)(CH3)CH2-).

[0136] Furthermore, if any number of hydrogen atoms in these alkylene groups are substituted with -OC(=O)-CH3, an example of such a substituted alkylene group is one in which the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is replaced with -OC(=O)-CH3.

[0137] In particular, divalent linking group A 4 These are methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH2OH)) CH2CH2- is preferred, ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH2-), 2-hydroxyethylene group (-CH2CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH2OH)CH2-) is more preferred, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH2-), and 2-hydroxyethylene group (-CH2CH(OH)-) are particularly preferred.

[0138] In equation (8), Y 4 represents a divalent linking group, which represents -O- or -NH-, and is more preferably -O-.

[0139] In equation (8), r represents either 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0140] In equation (8), E 1 This represents a hydroxyl group, a carboxyl group, or an oxirane group. E 1 When the group is an oxirane group, examples include ethylene oxide, 1,2-propylene oxide, and 1,3-propylene oxide. Among these, ethylene oxide is preferred.

[0141] In equation (8), s represents either 0 or 1. When s is 0, (-Y 4 -A 4 -) represents a single bond. When r is 0 and s is 0, E is present in the main chain of the repeating unit. 1This results in a structure where these elements are joined together.

[0142] The following structures are examples of preferred repeating units represented by equation (8).

[0143] [ka]

[0144] In equation (8), E 1 If is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (8) imparts solubility of the fluororesin (B) to alkaline developer. Therefore, if you want to impart alkali developability to a film obtained from the fluororesin (B), add E to the fluororesin (B) of this disclosure. 1 It is preferable to include a repeating unit represented by formula (8) when is a hydroxyl group or a carboxyl group.

[0145] A fluororesin (B) having crosslinked sites can be synthesized, for example, by polymerizing monomers to obtain a fluororesin precursor having repeating units consisting of the structures shown in formulas (3), (6) to (8) above, and then reacting the fluororesin precursor with a photopolymerizable group derivative to introduce photopolymerizable groups into the side chains of the polymer, thereby synthesizing a fluororesin (B) having repeating units consisting of the structures shown in formulas (4) and (5) above. The photopolymerizable groups introduced into the fluororesin precursor are preferably acrylic groups, methacrylic groups, vinyl groups, and allyl groups, with acrylic groups being more preferred. When introducing an acrylic group as a photopolymerizable group, examples of photopolymerizable group derivatives include acrylic acid derivatives such as isocyanate monomers having an acrylic group and epoxy monomers having an acrylic group. Examples of isocyanate monomers having an acrylic group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2-(2-methacryloyloxyethyl oxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Preferably, it is 2-isocyanatoethyl acrylate. Examples of epoxy monomers having an acrylic group include glycidyl acrylate and 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Mitsubishi Chemical Corporation).

[0146] A photopolymerizable group is introduced into the fluororesin precursor through an addition reaction between the hydroxyl group present in the fluororesin precursor and the photopolymerizable group derivative. The proportion of photopolymerizable groups in the fluororesin (B) is preferably 10 mol% or more and 70 mol% or less. If the proportion of photopolymerizable groups is less than 10 mol%, the strength of the resin film and partition tends to decrease. If the proportion of photopolymerizable groups exceeds 70 mol%, it may become difficult to form a resin film by coating. More preferably, it is 15 mol% to 60 mol%.

[0147] In the photosensitive resin composition of this disclosure, the molecular weight of the fluororesin (B) is the mass-average molecular weight measured by high-performance 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 resin film or 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 resin film by coating.

[0148] The degree of dispersion (Mw / Mn) of the fluororesin (B) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

[0149] The fluororesin (B) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of dispersing each property appropriately rather than locally, a random copolymer is preferred.

[0150] Preferred embodiments of the fluororesin (B) in the photosensitive resin composition of this disclosure are as follows: <Aspect 1> A fluororesin (B) containing repeating units represented by the following formulas (3), (5), (6-1), and (7): Formula (3):R 1 and R 2 Rb is a hydrogen atom, and Rb is independently a fluorine atom, a difluoromethyl group, or a trifluoromethyl group. Formula (5):R 5 and R 6 Each of these independently consists of a hydrogen atom or a methyl group, W 2 is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A 2 , A 3 Each of them independently consists of an ethylene group and Y 2 and Y 3 H is -O-, n is 1, r is 1 Formula (6-1):R 9 is a methyl group, p is an integer of 2, q is an integer between 4 and 8, and X is a fluorine atom. Formula (7):R 10 is a hydrogen atom, B is a hydroxyl group or carboxyl group, m is 1

[0151] <Aspect 2> A fluororesin (B) containing repeating units represented by the following formulas (5), (6), (6-1), and (8): Formula (5):R 5 and R 6 Each of these independently consists of a hydrogen atom or a methyl group, W 2is -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-, A 2 , A 3 is each independently an ethylene group, Y 2 and Y 3 is -O-, n is 1, r is 1 Formula (6): R 7 is a methyl group, R 8 is a branched perfluoroalkyl group having 3 to 15 carbon atoms Formula (6-1): R 9 is a methyl group, p is an integer of 2, q is an integer of 4 to 8, X is a fluorine atom Formula (8): R 13 is a methyl group, A 4 is an ethylene group, Y 4 is -O-, r is 1, s is 0 or 1, E 1 is a hydroxyl group or a carboxyl group

[0152] In the photosensitive resin composition of the present disclosure, the fluorine content of the fluorine-containing resin (B) is preferably 20 to 50% by mass, and more preferably 25 to 40% by mass. If the fluorine content is within this range, it is easily soluble in a solvent. Since the fluorine-containing resin (B) contains fluorine atoms, a resin film or bank excellent in liquid repellency can be obtained.

[0153] In the present specification, the "fluorine content of the fluorine-containing resin (B)" means a value calculated from the molar ratio of the monomers constituting the fluorine-containing resin (B) measured by NMR (nuclear magnetic resonance spectroscopy), the molecular weight of the monomers constituting the fluorine-containing resin (B), and the fluorine content contained in the monomers. Here, as an example, a method for measuring the fluorine content when the fluorine-containing resin (B) is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene and 2-(perfluorohexyl)ethyl methacrylate will be described. (i) First, by measuring the fluorine-containing resin (B) by NMR, the ratio of each composition is calculated (molar ratio). (ii) Multiply the molecular weight (Mw) of each monomer in the composition of the fluororesin (B) by its molar ratio, add up the resulting values, 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 4-hydroxystyrene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432. (iii) Next, calculate the fluorine content in the monomer in the fluorine-containing composition. (iv) Calculate the value of "fluorine content in monomer ÷ monomer molecular weight (Mw) × weight percentage (wt%)" for each component, and sum up the obtained values. (v) Calculate the fluorine content of the fluororesin (B) by dividing the value obtained in (iv) above by the total value obtained in (ii) above.

[0154] In the photosensitive resin composition of this disclosure, one or more types of fluororesin (B) can be used. The proportion of fluororesin (B) in the total solid content of the photosensitive resin composition of this disclosure is preferably 0.1 to 40% by mass, and more preferably 1 to 30% by mass. Within this range, the water-repellent and oil-repellent properties of the resin film and the adhesion to the substrate are good.

[0155] <Solvent> In the photosensitive resin composition of this disclosure, the solvent is not particularly limited as long as it is soluble in the fluororesin (B), and examples include the same solvent that can be used in the synthesis of the fluororesin (A) described above. Preferably, the solvent is methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone.

[0156] 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 (B) (however, if the photosensitive resin composition contains the alkali-soluble resin (D) described later, the concentration of the alkali-soluble resin (D) is included). 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 a bank can be obtained.

[0157] <Photopolymerization initiator> In the photosensitive resin composition of this disclosure, the photopolymerization initiator 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.

[0158] 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.

[0159] Examples of photoradical initiators include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based compounds.

[0160] 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.

[0161] 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.

[0162] Examples of diketone compounds include 4,4'-dimethoxybenzyl, methyl benzoylmate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylmate are preferred.

[0163] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0164] Examples of quinone compounds include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0165] 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.

[0166] As photoradical initiators, benzophenone-based, acetophenone-based, and diketone-based agents are preferred, with benzophenone-based agents being more preferred.

[0167] Among commercially available photoradical initiators, preferred examples include products from BASF Co., Ltd.: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, and Lucilin TPO. Of these, Irgacure 651 and Irgacure 369 are more preferred.

[0168] 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.

[0169] Examples of commercially available photoacid generators 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 Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, Cyracure Photocuring Initiator UVI-6976; and ADEKA Corporation's product names: ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, ADEKA Optomer SP Examples include -172, Adeka Optomer SP-300, products from Nippon Soda Co., Ltd.: CI-5102, CI-2855, products from Sanshin Chemical Industry Co., Ltd.: Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180, products from Lamberti: Esacure 1064, Esacure 1187, and products from Ciba Specialty Chemicals Co., Ltd.: Irgacure 250.

[0170] 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 (B) (however, if the photosensitive resin composition contains the alkali-soluble resin (D) described later, the amount of the alkali-soluble resin (D) is 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.

[0171] The photosensitive resin composition of this disclosure preferably further comprises an ethylenically unsaturated compound (C) and / or an alkali-soluble resin (D). <Ethylene-unsaturated compounds (C)> When the photosensitive resin composition of this disclosure contains an ethylenically unsaturated compound (C), the curing of the photosensitive resin composition by light irradiation is accelerated, enabling curing in a shorter time. Specific examples of ethylenically unsaturated compounds (C) 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.

[0172] The following are examples of preferred polyfunctional acrylate compounds.

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] The content of the ethylenically unsaturated compound (C) 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 concentration of the fluororesin (B) (however, if the photosensitive resin composition contains the alkali-soluble resin (D) described later, the total amount of the alkali-soluble resin (D) is included). When the content of ethylenically unsaturated compounds (C) is less than 10 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and when it exceeds 300 parts by mass, the resolution and sensitivity tend to decrease.

[0177] <Alkali-soluble resin (D)> If the photosensitive resin composition of this disclosure contains an alkali-soluble resin (D), the shape of the bank obtained from the photosensitive resin composition of this disclosure can be improved. Examples of alkali-soluble resins (D) include alkali-soluble novolac resins. Alkali-soluble novolac resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

[0178] 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.

[0179] 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.

[0180] Other examples of alkali-soluble resins (D) 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, ZAR2051H, ZFR-1185, and ZCR-1569H.

[0181] The weight-average molecular weight of the alkali-soluble resin (D) component is preferably 1,000 to 50,000 from the viewpoint of developability and resolution of the photosensitive resin composition.

[0182] The content of the alkali-soluble resin (D) 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 (B). If the content of the alkali-soluble resin (D) exceeds 10,000 parts by mass, the liquid-repellent properties of the fluororesin of this disclosure to ink after UV ozone treatment or oxygen plasma treatment tend not to be sufficiently obtained.

[0183] The photosensitive resin composition of the present disclosure preferably further comprises at least one selected from the group consisting of a photoradical sensitizer (E), a chain transfer agent (F), an ultraviolet absorber (G), and a polymerization inhibitor (H).

[0184] <Photoradical sensitizer (E)> The exposure sensitivity of the photosensitive resin composition of this disclosure can be further improved if it contains a photoradical sensitizer (E). The photoradical sensitizer (E) is preferably a compound that absorbs light or radiation and becomes excited. When the photoradical sensitizer (E) becomes excited, it causes electron transfer, energy transfer, or heat generation when it comes into contact with a photopolymerization initiator, which makes the photopolymerization initiator more likely to decompose and generate acid. The photoradical sensitizer (E) only needs to have an absorption wavelength in the region of 350 nm to 450 nm, and examples include polynuclear aromatics, xanthenes, xanthones, cyanines, merocyanines, thiaidines, acridines, acridons, anthraquinones, squariums, styryls, base styryls, or coumarins.

[0185] Examples of polynuclear aromatics include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, or 9,10-dipropyloxyanthracene.

[0186] Examples of xanthenes include fluorescein, eosin, erythrosine, rhodamine B, and rose bengal. Examples of xanthones include xanthones, thioxanthones, dimethylthioxanthones, diethylthioxanthones, or isopropylthioxanthones.

[0187] Examples of cyanines include thiacarbocyanin and oxacarbocyanin. Examples of merocyanines include merocyanine and carbomerocyanine. Examples of thiazines include thionine, methylene blue, and toluidine blue.

[0188] Examples of acridines include acridine orange, chloroflavin, and acriflavin. Examples of the acridones include acridone and 10-butyl-2-chloroacridone.

[0189] Examples of the anthraquinones include anthraquinone. Examples of the squariliums include squarilium. Examples of the base styryls include 2-[2-[4-(dimethylamino)phenyl]ethenyl]benzoxazole.

[0190] Examples of the coumarins include 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, or 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[l]benzopyrano[6,7,8-ij]quinolizin-11-one. These photo radical sensitizers (E) may be used alone or in combination of two or more.

[0191] As the photo radical sensitizer (E) used in the photosensitive resin composition of the present disclosure, polycyclic aromatics, acridones, styryls, base styryls, coumarins, or xanthones are preferable because of the great effect of improving the exposure sensitivity, and xanthones are particularly preferable. Among the xanthones, diethylthioxanthone and isopropylthioxanthone are preferable.

[0192] The content of the photo radical sensitizer (E) is preferably 0.1 part by mass to 8 parts by mass, more preferably 1 part by mass to 4 parts by mass, based on 100 parts by mass of the fluorine-containing resin (B). By setting the content of the photo radical sensitizer (E) within the above range, the exposure sensitivity of the photosensitive resin composition is improved, the boundary between the liquid-repellent part and the liquid-affinitive part in the pattern forming film after exposing the photosensitive resin composition of the present disclosure becomes clear, the contrast of the ink pattern after ink application is improved, and a fine pattern can be obtained.

[0193] <Chain transfer agent (F)> It is preferable to use a chain transfer agent (F) in the photosensitive resin composition of the present disclosure as needed. Examples of the chain transfer agent (F) include the same compounds that can be used in the synthesis of the fluororesin (A) described above.

[0194] <UV absorber (G)> The photosensitive resin composition of this disclosure preferably contains an ultraviolet absorber (G) as needed, and examples of ultraviolet absorbers (G) include salicylic acid-based, benzophenone-based, and triazole-based materials. The content of the ultraviolet absorber (G) in the photosensitive resin composition is preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass.

[0195] <Polymerization inhibitor (H)> The polymerization inhibitor (H) used in the photosensitive resin composition of this disclosure is not particularly limited, but examples include o-cresol, m-cresol, p-cresol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butyl-p-cresol, hydroquinone, catechol, 4-t-butylpyrocatechol, 2,5-bistetramethylbutylhydroquinone, 2,5-di-t-butylhydroquinone, p-methoxyphenol, 1,2,4-trihydroxybenzene, 1,2-benzoquinone, 1,3-benzoquinone, 1,4-benzoquinone, leucoquinizarin, phenothiazine, 2-methoxyphenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, or 1,1-diphenyl-2-picrylhydrazine.

[0196] Examples of commercially available polymerization inhibitors (H) include N,N'-di-2-naphthyl-p-phenylenediamine (trade name, Nonflex F), N,N-diphenyl-p-phenylenediamine (trade name, Nonflex H), 4,4'-bis(a,a-dimethylbenzyl)diphenylamine (trade name, Nonflex DCD), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) (trade name, Nonflex MBP), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name, Ozonone 35), manufactured by Seiko Chemicals Ltd., or ammonium N-nitrosophenylhydroxyamine (trade name, Q-1300) or N-nitrosophenylhydroxyamine aluminum salt (trade name, Q-1301), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0197] The content of polymerization inhibitor (H) in the total solids of the photosensitive resin composition of this disclosure is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, and particularly preferably 0.01 to 5% by mass. When the content is within the above range, the development residue of the photosensitive resin composition is reduced and the pattern linearity is good.

[0198] The photosensitive resin composition of this disclosure may contain other additives as needed. Examples of other additives include various additives such as dissolution inhibitors, plasticizers, stabilizers, colorants, thickeners, adhesives, and antioxidants. These other additives may be known.

[0199] The cured product of this disclosure is characterized by being obtained by curing a photosensitive resin composition. The photosensitive resin composition of this disclosure can be formed by a known method and exposed to light to obtain a "resin film" which is a film made of a cured product of a composition mainly composed of a fluororesin (B). The specific methods of film formation and exposure are the same as the method for forming a partition described later. The resin film obtained from the photosensitive resin composition of this disclosure has improved surface roughness due to the inclusion of the above-mentioned surface modifier. The cured product of this disclosure is preferably used as a partition, and is particularly preferably used as a partition in organic EL displays, quantum dot displays, and the like.

[0200] 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.

[0201] (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.

[0202] 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).

[0203] As a method for applying the photosensitive resin composition of this disclosure to a substrate, known methods such as spin coating can be used.

[0204] (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 ray is preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0205] The exposure dose of the high-energy ray is preferably 1 mJ / cm 2 or more and 200 mJ / cm 2 or less, more preferably 10 mJ / cm 2 or more and 100 mJ / cm 2 or less.

[0206] (3) Development process Next, the fluororesin film after the exposure process is developed with an alkaline aqueous solution to obtain a fluororesin pattern film. That is, either the exposed portion or the unexposed portion of the fluororesin film is dissolved in an alkaline aqueous solution to obtain a fluororesin pattern film.

[0207] As the alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), or the like can be used. When the alkaline aqueous solution is an aqueous solution of tetramethylammonium hydroxide (TMAH), its concentration is preferably 0.1 mass% or more and 5 mass% or less, more preferably 2 mass% or more and 3 mass% or less.

[0208] Known methods can be used for the development method, and examples thereof include a dip method, a paddle method, a spray method, and the like.

[0209] The development time (the time during which the developer contacts the fluororesin film) is preferably 10 seconds or more and 3 minutes or less, more preferably 30 seconds or more and 2 minutes or less.

[0210] After development, if necessary, a step of washing the fluororesin pattern film with deionized water or the like may be provided. Regarding the washing method and the washing time, it is preferably 10 seconds or more and 3 minutes or less, more preferably 30 seconds or more and 2 minutes or less.

[0211] The bulkheads manufactured in this way can be used as display banks.

[0212] The display of the present disclosure is characterized by including a light-emitting element comprising a partition obtained by curing the photosensitive resin composition of the present disclosure, and a light-emitting layer or wavelength conversion layer disposed in a region partitioned by the partition. Examples of displays include organic EL displays and quantum dot displays.

[0213] The surface treatment method for molded articles according to this disclosure is characterized by using a fluororesin (A) having the structure represented by the above general formula (1). The fluororesin (A) can be the same as that described above for the surface modifier and photosensitive resin composition. The method disclosed herein allows for surface preparation of various resin molded articles. Surface preparation of molded articles involves suppressing the occurrence of various coating defects such as bubbles, brush marks, orange peel, blemishes, craters, pinholes, and uneven lifting that occur during resin molding or coating production. By suppressing the occurrence of these coating defects, for example, surface roughness can be improved. The type of resin used as the material for the molded article is not particularly limited, and examples include one or more types of olefin resins, epoxy resins, (meth)acrylic resins, urethane resins, fluororesins, etc. The method disclosed herein is particularly suitable for use when producing molded articles with a composition containing two or more resins with different fluorine content. A photosensitive resin composition is particularly preferred as the composition. In the method of this disclosure, the fluororesin (A) can be used by mixing it with the resin composition. The preferred embodiment and amount of the fluororesin (A) are the same as those for the photosensitive resin composition described above. Fluorine-containing resin (A) acts as a surface modifier and surfactant, such as an antifoaming agent, leveling agent, and anti-wrinkle agent.

[0214] This disclosure also includes the use of the fluororesin (A) having the structure represented by the above general formula (1) for adjusting the surface of a molded article.

Examples

[0215] Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these examples.

[0216] [Measurement of the molar ratio of each repeating unit in the polymer] The molar ratio of each repeating unit in the polymer was 1 determined from the measurement values of H-NMR, 19 F-NMR or 13 C-NMR.

[0217] [Measurement of the molecular weight of the polymer] The weight average molecular weight Mw and the molecular weight distribution (the ratio of the weight average molecular weight Mw to the number average molecular weight Mn; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC; manufactured by Tosoh Corporation, model HLC-8320GPC), connecting one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) in series, using polystyrene as a standard substance, and using tetrahydrofuran (THF) as a developing solvent. A differential refractive index detector was used as the detector.

[0218] 1. Synthesis of fluororesin (B) Synthesis Example 1 Synthesis of fluororesin B-1 having a crosslinking site [Synthesis of fluororesin precursor 1] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 4.3 g (0.02 mol) of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd., hereinafter referred to as BTFBE), 2.7 g (0.02 mol) of 4-acetoxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 21.4 g (0.07 mol) of 2-(perfluorobutyl)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C4F), 6.1 g (0.05 mol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HEMA), and 36.9 g of methyl ethyl ketone (hereinafter referred to as MEK) were taken. 2.46 g (0.02 mol) of 2,2'-azobis(2-methylbutyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 79 °C and reacted overnight. When 250 g of n-heptane was dropped into the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45 °C to obtain 30.4 g of a fluorine-containing resin precursor 1 as a white solid with a yield of 88%.

[0219] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 1, expressed in mol ratio, was repeating unit by BTFBE: repeating unit by p-AcO-St: repeating unit by MA-C4F: repeating unit by HEMA = 15:11:43:31.

[0220] [Chemical formula]

[0221] <GPC measurement results> Mw = 7,201, Mw / Mn = 1.4

[0222] [Synthesis of fluorine-containing resin B-1 having a crosslinked site] In a 100 ml glass flask equipped with a stirrer, 10 g of fluororesin precursor 1 (hydroxyl equivalent 0.01 mol), 0.07 g of triethylamine (hydroxyl equivalent 0.0007 mol), and 20 g of PGMEA were taken. 1.51 g of Karenz-AOI (2-isocyanatoethyl acrylate, manufactured by Showa Denko K.K.) (hydroxyl equivalent 0.01 mol) was added, and the mixture was reacted at 45°C for 4 hours. After the reaction was complete, the reaction solution was concentrated, and 100 g of n-heptane was added to precipitate. This precipitate was filtered off and dried under reduced pressure at 40°C to obtain fluororesin B-1 with crosslinking sites as a white solid in 75% yield.

[0223] [ka]

[0224] < 13 C-NMR measurement results> In fluororesin B-1, which has crosslinked sites, the amount of acrylic acid derivative derived from currant-AOI introduced (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 crosslinked sites (repeating units due to BTFBE, repeating units due to p-AcO-St, and repeating units due to MA-C4F) remained unchanged from that of the fluororesin precursor 1 used (the same as before the introduction of the crosslinked sites).

[0225] Synthesis Example 2: Synthesis of fluororesin B-2 having crosslinking sites [Synthesis of Fluorine-containing Resin Precursor 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 2-(perfluorohexyl)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 23.6 g (0.1 mol) of hexafluoroisopropyl methacrylate (manufactured by Central Glass Co., Ltd.; hereinafter referred to as HFIP-M), 8.66 g (0.1 mol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MAA), and 88 g of MEK were taken. After adding 1.6 g (0.010 mol) of AIBN and degassing while stirring, the inside of the flask was replaced with nitrogen gas, and after heating to 80 °C, the reaction was carried out for 6 hours. When the reaction solution after the completion of 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 fluorine-containing resin precursor 2 as a white solid with a yield of 68%.

[0226] <NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 2, expressed as a mol ratio, was: repeating unit by HEMA: repeating unit by MA-C6F: repeating unit by HFIP-M: repeating unit by MAA = 24:26:24:26.

[0227]

Chemical formula

[0228] <GPC measurement results> Mw = 10,700, Mw / Mn = 1.5

[0229] [Synthesis of fluorine-containing resin B-2 having a crosslinked site] A fluorine-containing resin B-2 having a crosslinked site was obtained in a yield of 90% by the same procedure as the synthesis of the fluorine-containing resin B-1 having a crosslinked site, except that the fluorine-containing resin precursor 2 was used instead of the fluorine-containing resin precursor 1.

[0230] < 13 <C-NMR measurement results> In the fluororesin B-2 having a crosslinked site, the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz-AOI and the amount of remaining hydroxyl groups (unreacted rate) were 96:4 in terms of mol ratio. Also, it was confirmed that the composition ratios of each repeating unit that does not react with the crosslinked site (the repeating unit by MA-C6F, the repeating unit by HFIP-M) did not change from the fluororesin precursor 2 used (the same as before the introduction of the crosslinking group).

[0231] 2. Synthesis of the fluororesin (A) for the surface conditioner Example 1 [Synthesis of fluororesin A-1] At room temperature (about 20 °C) in a 100 ml glass flask equipped with a stirrer, 11.8 g (0.04 mol) of 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl methacrylate (manufactured by Central Glass Co., Ltd.; hereinafter referred to as MA-BTHB-OH), 24 g of MEK were taken, 0.65 g (0.004 mol) of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and the internal temperature was raised to 79 °C and reacted for 6 hours. When 200 g of n-heptane was dropped into the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at a temperature of 45 °C to obtain 8.47 g of fluororesin A-1 as a white solid with a yield of 72%.

[0232]

Chemical formula

[0233] <GPC measurement result> Mw = 13,370, Mw / Mn = 1.9

[0234] Example 2 [Synthesis of fluororesin A-2] Fluororesin A-2 was obtained with a yield of 68% in the same procedure as the synthesis of fluororesin A-1 except that the internal temperature was raised to 85 °C.

[0235] <GPC measurement result> Mw = 8770, Mw / Mn = 1.6

[0236] Example 3 [Synthesis of Fluorine-containing Resin A-3] A fluorine-containing resin A-3 was obtained in a yield of 87% by the same procedure as the synthesis of the fluorine-containing resin A-1, except that 0.16 g (0.001 mol) of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

[0237] [GPC Measurement Results] Mw = 38,400, Mw / Mn = 2.3

[0238] Example 4 [Synthesis of Fluorine-containing Resin A-4] A fluorine-containing resin A-4 was obtained in a yield of 84% by the same procedure as the synthesis of the fluorine-containing resin A-1, except that 3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate (manufactured by Central Glass Co., Ltd.) was used instead of MA-BTHB-OH.

[0239] [Chemical Structure]

[0240] [GPC Measurement Results] Mw = 14,800, Mw / Mn = 1.9

[0241] Example 5 [Synthesis of Fluorine-containing Resin A-5] A fluorine-containing resin A-5 was obtained in a yield of 82% by the same procedure as the synthesis of the fluorine-containing resin A-1, except that 1,3-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl) isopropyl methacrylate (manufactured by Central Glass Co., Ltd., hereinafter referred to as MA-BTHB-HFA) was used instead of MA-BTHB-OH.

[0242] [Chemical Structure]

[0243] <GPC measurement result> Mw = 11,800, Mw / Mn = 1.5

[0244] Example 6 [Synthesis of fluororesin A-6] In a 300 ml glass flask equipped with a stirrer at room temperature (about 20 °C), 13.86 g (0.3 mol) of MA-BTHB-HFA, 2.36 g (0.1 mol) of HFIP-M, and 32 g of MEK were taken, 0.25 g (0.002 mol) of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 79 °C and reacted overnight. When 200 g of n-heptane was dropped into the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at 50 °C to obtain 13 g of fluororesin A-6 as a white solid with a yield of 80%.

[0245] <NMR measurement result> The composition ratio of each repeating unit of fluororesin A-6, expressed in molar ratio, was repeating unit by MA-BTHB-HFA: repeating unit by HFIP-M = 75:25.

[0246]

Chemical formula

[0247] <GPC measurement result> Mw = 12,300, Mw / Mn = 1.6

[0248] Example 7 [Synthesis of fluororesin A-7] Fluororesin A-7 was obtained with a yield of 81% in the same procedure as the synthesis of fluororesin A-6, except that butyl methacrylate (Tokyo Chemical Industry reagent) was used instead of HFIP-M.

[0249] <NMR measurement result> The composition ratio of each repeating unit of fluororesin A-7, expressed in molar ratio, was repeating unit by MA-BTHB-HFA: repeating unit by butyl methacrylate = 75:25.

[0250]

Chemical formula

[0251] <GPC measurement results> Mw = 11,300, Mw / Mn = 1.5

[0252] Example 8 [Synthesis of fluororesin A-8] Fluororesin A-8 was obtained in a yield of 79% by the same procedure as the synthesis of fluororesin A-6, except that 4.62 g (0.1 mol) of MA-BTHB-HFA and 7.08 g (0.3 mol) of HFIP-M were changed.

[0253] <NMR measurement results> The composition ratio of each repeating unit of fluororesin A-8, expressed in molar ratio, was repeating unit by MA-BTHB-HFA: repeating unit by HFIP-M = 25:75.

[0254]

Chemical formula

[0255] <GPC measurement results> Mw = 13,000, Mw / Mn = 1.7

[0256] Example 9 [Synthesis of fluororesin A-9] Fluororesin A-9 was obtained in a yield of 82% by the same procedure as the synthesis of fluororesin A-6, except that 9.24 g (0.2 mol) of MA-BTHB-HFA and 4.72 g (0.2 mol) of HFIP-M were changed.

[0257] <NMR measurement results> The composition ratio of each repeating unit of fluororesin A-9, expressed as a molar ratio, was the repeating unit by MA-BTHB-HFA: the repeating unit by HFIP-M = 50:50.

[0258]

Chemical formula

[0259] <GPC measurement result> Mw = 12,500, Mw / Mn = 1.6

[0260] Example 10 [Synthesis of fluororesin A-10] At room temperature (about 20°C) in a 300 ml glass flask equipped with a stirrer, 14.62 g (0.1 mol) of MA-BTHB-HFA, 2.36 g (0.1 mol) of HFIP-M, 1.42 g (0.1 mol) of butyl methacrylate, and 36 g of MEK were taken, 0.25 g (0.002 mol) of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and heated to an internal temperature of 79°C and reacted overnight. When 200 g of n-heptane was dropped into the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at 50°C to obtain 14 g of fluororesin A-10 as a white solid with a yield of 76%.

[0261] <NMR measurement result> The composition ratio of each repeating unit of fluororesin A-10, expressed as a molar ratio, was the repeating unit by MA-BTHB-HFA: the repeating unit by HFIP-M: the repeating unit by butyl methacrylate = 1:1:1.

[0262]

Chemical formula

[0263] <GPC measurement result> Mw = 13,800, Mw / Mn = 1.8

[0264] Comparative Example 1 [Synthesis of Fluorine-containing Resin A-1 for Comparison] Except for using HFIP-M (manufactured by Central Glass Co., Ltd.) instead of MA-BTHB-OH, Comparative Fluorine-containing Resin A-1 was obtained in a yield of 81% by the same procedure as the synthesis of Fluorine-containing Resin A-1.

[0265]

Chemical Structure

[0266] <GPC Measurement Results> Mw = 12,123, Mw / Mn = 1.8

[0267] Comparative Example 2 [Synthesis of Fluorine-containing Resin A-2 for Comparison] At room temperature (about 20 °C), 16.6 g (0.07 mol) of HFIP-M (manufactured by Central Glass Co., Ltd.), 4.0 g (0.03 mol) of HEMA (manufactured by Tokyo Chemical Industry Co., Ltd.), and 20 g of MEK were placed in a 100 ml glass flask equipped with a stirrer. 0.17 g (0.001 mol) of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after degassing while stirring, the inside of the flask was replaced with nitrogen gas and heated to an internal temperature of 80 °C and reacted overnight. When 160 g of n-heptane was dropped into the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at a temperature of 45 °C to obtain 17.0 g of Comparative Fluorine-containing Resin A-2 as a white solid in a yield of 83%.

[0268] <NMR Measurement Results> The composition ratio of each repeating unit of Comparative Fluorine-containing Resin A-2, expressed as a molar ratio, was: repeating unit by HFIP-M: repeating unit by HEMA = 70:30.

[0269]

Chemical Structure

[0270] <0确定]] <GPC Measurement Results> Mw = 14,289, Mw / Mn = 1.7

[0271] 3. Preparation of photosensitive resin composition Comparative Example 3 [Preparation of photosensitive resin composition 1] A photosensitive resin composition 1 was prepared by blending 0.5 parts by mass of fluororesin B-1 having a manufactured crosslinked portion, 0.5 parts by mass of Irgacure 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, product of BASF Co., Ltd.) as a polymerization 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 (bisphenol A type epoxy acrylate, 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.

[0272] Example 11 [Preparation of photosensitive resin composition 1-1] To the photosensitive resin composition 1 prepared above, fluororesin A-1 obtained in "2. Synthesis of fluororesin for surface modifier" was added in the proportion (mass%) shown in Table 1 relative to the total solid content of photosensitive resin composition 1 and dissolved. After dissolving, the resulting solution was filtered through a 0.2 μm membrane filter to prepare photosensitive resin composition 1-1.

[0273] Example 12 [Preparation of photosensitive resin compositions 1-2] Photosensitive resin composition 1-2 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-2 was used instead of fluororesin A-1.

[0274] Example 13 [Preparation of photosensitive resin compositions 1-3] Photosensitive resin composition 1-3 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-3 was used instead of fluororesin A-1.

[0275] Example 14 [Preparation of photosensitive resin compositions 1-4] Photosensitive resin composition 1-4 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-4 was used instead of fluororesin A-1.

[0276] Example 15 [Preparation of photosensitive resin compositions 1-5] Photosensitive resin composition 1-5 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-5 was used instead of fluororesin A-1.

[0277] Example 16 [Preparation of photosensitive resin compositions 1-6] Photosensitive resin composition 1-6 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-6 was used instead of fluororesin A-1.

[0278] Example 17 [Preparation of photosensitive resin compositions 1-7] Photosensitive resin composition 1-7 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-7 was used instead of fluororesin A-1.

[0279] Example 18 [Preparation of photosensitive resin compositions 1-8] Photosensitive resin composition 1-8 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-8 was used instead of fluororesin A-1.

[0280] Example 19 [Preparation of photosensitive resin compositions 1-9] Photosensitive resin composition 1-9 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-9 was used instead of fluororesin A-1.

[0281] Example 20 [Preparation of photosensitive resin compositions 1-10] Photosensitive resin composition 1-10 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that fluororesin A-10 was used instead of fluororesin A-1.

[0282] Comparative Example 4 [Preparation of comparative photosensitive resin composition 1-1] The comparative photosensitive resin composition 1-1 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that comparative fluororesin A-1 was used instead of fluororesin A-1.

[0283] Comparative Example 5 [Preparation of comparative photosensitive resin compositions 1-2] Comparative photosensitive resin composition 1-2 was prepared using the same procedure as for the preparation of photosensitive resin composition 1-1, except that comparative fluororesin A-2 was used instead of fluororesin A-1.

[0284] Comparative Example 6 [Preparation of photosensitive resin composition 2] A photosensitive resin composition 2 was prepared by blending 0.5 parts by mass of the manufactured fluororesin B-2 having crosslinked sites, 0.5 parts by mass of Irgacure 369 as a polymerization initiator, 50 parts by mass of pentaerythritol tetraacrylate as a crosslinking agent, 50 parts by mass of ZAR2051H as an alkali-soluble resin, and 160 parts by mass of PGMEA and 70 parts by mass of PGME as solvents, and filtering the resulting solution through a 0.2 μm membrane filter.

[0285] Example 21 [Preparation of photosensitive resin composition 2-1] To the photosensitive resin composition 2 prepared above, fluororesin A-1 obtained in "2. Synthesis of fluororesin for surface modifier" was added in the proportion (mass%) shown in Table 1 relative to the total solid content of photosensitive resin composition 2 and dissolved. After dissolving, the resulting solution was filtered through a 0.2 μm membrane filter to prepare photosensitive resin composition 2-1.

[0286] Example 22 [Preparation of photosensitive resin composition 2-2] Photosensitive resin composition 2-2 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-2 was used instead of fluororesin A-1.

[0287] Example 23 [Preparation of photosensitive resin compositions 2-3] Photosensitive resin composition 2-3 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-3 was used instead of fluororesin A-1.

[0288] Example 24 [Preparation of photosensitive resin compositions 2-4] Photosensitive resin composition 2-4 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-4 was used instead of fluororesin A-1.

[0289] Example 25 [Preparation of photosensitive resin compositions 2-5] Photosensitive resin composition 2-5 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-5 was used instead of fluororesin A-1.

[0290] Example 26 [Preparation of photosensitive resin compositions 2-6] Photosensitive resin composition 2-6 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-6 was used instead of fluororesin A-1.

[0291] Example 27 [Preparation of photosensitive resin compositions 2-7] Photosensitive resin composition 2-7 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-7 was used instead of fluororesin A-1.

[0292] Example 28 [Preparation of photosensitive resin compositions 2-8] Photosensitive resin composition 2-8 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-8 was used instead of fluororesin A-1.

[0293] Example 29 [Preparation of photosensitive resin compositions 2 and 9] Photosensitive resin composition 2-9 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-9 was used instead of fluororesin A-1.

[0294] Example 30 [Preparation of photosensitive resin compositions 2-10] Photosensitive resin composition 2-10 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that fluororesin A-10 was used instead of fluororesin A-1.

[0295] Comparative Example 7 [Preparation of comparative photosensitive resin composition 2-1] The comparative photosensitive resin composition 2-1 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that comparative fluororesin A-1 was used instead of fluororesin A-1.

[0296] Comparative Example 8 [Preparation of comparative photosensitive resin composition 2-2] The comparative photosensitive resin composition 2-2 was prepared using the same procedure as for the preparation of photosensitive resin composition 2-1, except that comparative fluororesin A-2 was used instead of fluororesin A-1.

[0297] 4. Evaluation of surface roughness Using the photosensitive resin compositions 1, 1-1 to 1-10, 2, 2-1 to 2-10, and comparative photosensitive resin compositions 1-1 to 1-2 and 2-1 to 2-2 obtained in "3. Preparation of Photosensitive Resin Compositions," resin films were prepared, and their surface roughness was evaluated and compared. The results are shown in Table 1.

[0298] [Formation of resin film] A 10 cm square alkali-free substrate was washed with ultrapure water, followed by acetone. 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, the photosensitive resin compositions 1, 1-1~1-10, 2, 2-1~2-10, and comparative photosensitive resin compositions 1-1~1-2, 2-1~2-2 obtained in "3. Preparation of Photosensitive Resin Compositions" were applied to the UV ozone-treated substrate using a spin coater at a rotation speed of 1,000 rpm. The mixture was then 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. The resulting resin films were irradiated with i-line light (wavelength 365 nm) to perform exposure. The resulting exposed resin film was heated at 230°C for 60 minutes. After cooling the entire substrate, the surface roughness was evaluated by measuring 10 points within a 1 mm square area using a laser microscope (Keyence VX-1100) with a 150x objective lens to calculate the arithmetic mean roughness.

[0299] [Table 1]

[0300] As shown in Table 1, the resin films obtained using the comparative example's photosensitive resin composition had a surface roughness of 90 nm or more, while the resin films obtained using the example's photosensitive resin composition all had a surface roughness of 10 to 60 nm, clearly demonstrating significant superiority compared to the comparative example.

[0301] 5. Bank's evaluation Using the photosensitive resin compositions 1, 1-1 to 1-10, 2, 2-1 to 2-10, and comparative photosensitive resin compositions 1-1 to 1-2 and 2-1 to 2-2 obtained in "3. Preparation of Photosensitive Resin Compositions," banks 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 Tables 2 and 3. [Bank formation] A 10 cm square ITO substrate was washed with ultrapure water, then with acetone, and then subjected to UV ozone treatment for 5 minutes using the aforementioned UV ozone treatment apparatus. Next, using the photosensitive resin compositions 1, 1-1~1-10, 2, 2-1~2-10 and comparative photosensitive resin compositions 1-1~1-2, 2-1~2-2 obtained in "3. Preparation of Photosensitive Resin Compositions," the 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 2 μm thick fluororesin film and a comparative fluororesin film. Using a mask aligner (product of 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.

[0302] [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.

[0303] [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."

[0304] [Contact angle] After heating the substrate having the bank obtained by the above process at 230°C for 60 minutes, the anisole contact angle of the bank surface was measured.

[0305] [Surface roughness] The surface roughness of the bank was evaluated using a laser microscope. A Keyence VX-1100 laser microscope was used, and the evaluation was performed in the same manner as for the surface roughness of the resin film.

[0306] [Table 2]

[0307] [Table 3]

[0308] As shown in Tables 2 and 3, both the example bank and the comparative example bank were negative-type resists in which only the unexposed areas dissolved in developer solubility evaluation. In bank performance evaluation, they showed similar sensitivity, with 5 μm line and space of the mask being transferred with good resolution and no line edge roughness observed, resulting in a resolution rating of "excellent". The liquid repellency of anisole in the exposed areas also showed sufficient values. In other words, these evaluations showed that the surface modifiers of the example and the comparative example had little effect on the banks. On the other hand, in the comparative example bank, the surface roughness of the exposed area (upper part of the bank) was approximately 100 nm or more, while in the example bank, the surface roughness was 10-70 nm, clearly demonstrating significant superiority compared to the comparative example.

[0309] This application is based on Japanese Patent Application No. 2021-023616, filed on 17 February 2021, and claims priority under the Paris Convention or the laws of the country entering the transition. The contents of said application are incorporated in their entirety by reference in this application.

Claims

1. A surface modifier comprising a fluororesin (A) having a structure represented by the following general formula (1), a fluororesin (B) having a crosslinked portion, a solvent, and a photopolymerization initiator, A photosensitive resin composition in which the content of the fluororesin (A) is 0.1% by mass or more and 2.5% by mass or less based on the total solid content of the photosensitive resin composition. 【Chemistry 1】 (In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)

2. The photosensitive resin composition according to claim 1, wherein the content of the structure represented by general formula (1) in the fluororesin (A) is 50 mol% or more and 300 mol% or less, with the total amount of repeating units constituting the fluororesin (A) being 100 mol%.

3. The photosensitive resin composition according to claim 1 or 2, wherein the weight-average molecular weight of the fluororesin (A) is 5,000 or more and 40,000 or less.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein Ra in the general formula (1) is a trifluoromethyl group.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising an ethylenically unsaturated compound (C) and / or an alkali-soluble resin (D).

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of a photoradical sensitizer (E), a chain transfer agent (F), an ultraviolet absorber (G), and a polymerization inhibitor (H).

7. A photosensitive resin composition according to any one of claims 1 to 6, used for forming a partition wall.

8. A cured product characterized by being obtained by curing a photosensitive resin composition according to any one of claims 1 to 7.

9. A cured product according to claim 8, which is a partition wall.

10. A display comprising a light-emitting element comprising a surface modifier containing a fluororesin (A) having a structure represented by the following general formula (1), a fluororesin (B) having a crosslinked portion, a solvent, and a photopolymerization initiator, a partition obtained by curing the photosensitive resin composition, and a light-emitting layer or wavelength conversion layer disposed in a region partitioned by the partition. 【Chemistry 2】 (In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)

11. The display according to claim 10, which is an organic EL display or a quantum dot display.

12. A method for surface preparation of a molded article that is a partition wall that demarcates a region in which a light-emitting layer or wavelength conversion layer of a light-emitting element included in a display is located, using a fluororesin (A) having a structure represented by the following general formula (1). 【Transformation 3】 (In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)

13. Use of a fluororesin (A) having a structure represented by the following general formula (1) for adjusting the surface of a molded article which is a partition wall that demarcates a region in which an emissive layer or wavelength conversion layer of a light-emitting element included in a display is arranged. 【Chemistry 4】 (In general formula (1), Ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, wherein any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)

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