TW202229381A - Fluorine-containing resin, liquid repellent agent, photosensitive resin composition, cured product and display - Google Patents

Abstract

The present invention provides a fluorine-containing resin which is capable of forming a bank (a partition wall) that is not susceptible to a decrease in the liquid repellency even if subjected to an UV ozone treatment or an oxygen plasma treatment. A fluorine-containing resin according to the present invention is characterized by comprising a repeating unit (U) which contains, as a monomer unit, a monomer (A) that has a triple bond in a side chain.

Description

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

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

When manufacturing display elements such as organic EL (Electroluminescence) displays, micro-LED (light-emitting diode) displays, quantum dot displays, etc., as a method of forming an organic layer with functions such as light emission, it is known. There is an inkjet method. There are several methods of the inkjet method, and specifically, a method of curing ink dropped from a nozzle to a concave portion of a pattern film having concavities and convexities formed on a substrate; The liquid part and the liquid-repellent part, which is the part not wetted by the ink, drop the ink droplets on the pattern film formed on the substrate in advance, and the method of making the ink only adhere to the lyophilic part, etc.

In particular, in the method of curing the ink dropped from the nozzle to the concave portion of the pattern film as exemplified in the former, in order to produce such a pattern film having concavities and convexities, two methods are mainly employed. One is photolithography, which forms an exposed part and an unexposed part by exposing the surface of the photosensitive resist film coated on the substrate in a pattern, and uses a developer to dissolve and remove any part; the other is It is an imprint method using printing technology. Usually, after forming the patterned film with unevenness, the entire surface of the substrate is subjected to UV (ultraviolet, ultraviolet) ozone treatment or oxygen plasma treatment. Through the UV ozone treatment or oxygen plasma treatment, especially the residual organic matter in the concave portion of the pattern film can be removed, and the uneven wetting of the dripped ink can be reduced, thereby preventing the failure of the display element before it occurs.

The convex part of the pattern film which has the unevenness|corrugation formed is called a barrier rib (partition wall), and when an ink is dripped in the recessed part of a pattern film, the barrier rib functions as a barrier for preventing the ink from being mixed with each other. In order to improve the effect as a barrier, the substrate surface is required to be exposed in the recessed portion of the pattern film, the substrate surface is lyophilic for ink, and the upper surface of the barrier wall is liquid-repellent for ink.

As the resin for forming such a barrier, a fluorine-containing resin can be used. Liquid repellency is improved by using fluorine-containing resin.

Patent Document 1 discloses, as a resist composition containing a fluorine-containing resin, a resist composition comprising a monomer unit formed of a monomer represented by Formula 1, and The fluorine-containing resin (A) having a fluorine atom content of 7 to 35% by mass, and a photosensitive component that reacts to light having a wavelength of 100 to 600 nm, the above-mentioned total solid content of the resist composition is The ratio of the fluorine-containing resin (A) is 0.1 to 30% by mass, and the photosensitive component includes: a photoacid generator (B); an alkali-soluble resin (C) having a carboxyl group and/or a phenolic hydroxyl group; and an acid crosslinking The agent (D) is a compound having two or more groups capable of reacting with a carboxyl group or a phenolic hydroxyl group by the action of an acid. CH ₂ =C(R ¹ )COOXR ^f ･･･Formula 1 In Formula 1, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and X represents a divalent organic compound having 1 to 6 carbon atoms that does not contain a fluorine atom group, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms.

In Patent Document 2, as an ink-repellent agent containing a polymerized unit containing a fluorine atom, an ink-repellent agent is disclosed, which is characterized by comprising a polymer having a polymerized unit (b1) and a polymerized unit (b2), wherein the polymerized unit is (b1) an alkyl group having 20 or less carbon atoms having at least one hydrogen atom substituted with a fluorine atom (wherein the alkyl group includes those having etheric oxygen), the polymer unit (b2) has an ethylenic double bond, and the above The fluorine content of the ink repellant is 5 to 25% by mass, and the number average molecular weight is 500 or more and less than 10,000.

Patent Document 3 discloses, as a resist composition containing a fluorine-containing resin, a resist composition comprising a monomer unit formed of a monomer represented by Formula 1, having a Fluorine-containing resin (A) having an ethylenic double bond and a fluorine atom content of 7 to 35% by mass, and a photosensitive component that reacts to light having a wavelength of 100 to 600 nm, relative to the resist composition The total solid content, the ratio of the fluorine-containing resin (A) is 0.1 to 30% by mass, and the photosensitive component contains a photoradical initiator (E) and ethylene having an acidic group and two or more in 1 molecule. Alkali-soluble resin (F) with double bond. CH ₂ =C(R ¹ )COOXR ^f ･･･Formula 1 In Formula 1, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and X represents a divalent organic compound having 1 to 6 carbon atoms that does not contain a fluorine atom group, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms.

In Patent Document 4, as a negative photosensitive resin composition containing an ink repellant having a fluorine atom, a negative photosensitive resin composition is disclosed, characterized in that it contains an alkali-soluble resin having photocurability Or alkali-soluble monomer (A), photoradical polymerization initiator (B), photoacid generator (C), acid hardener (D), and ink repellant (E) having a fluorine atom, and the above The content rate of the said fluorine atom in the ink repellent (E) is 1-40 mass %, and the said ink repellent (E) has an ethylenic double bond.

Patent Document 5 discloses, as a photosensitive resin composition having good liquid repellency, a photosensitive resin composition comprising at least a fluorine-containing resin having a crosslinking site, a solvent, and a photopolymerization initiator. agent, and the above-mentioned fluorine-containing resin contains a repeating unit containing a hydrocarbon having a fluorine atom. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent No. 4474991 Patent Document 2: Japanese Patent No. 4488098 Patent Document 3: Japanese Patent No. 4905563 Patent Document 4: Japanese Patent No. 6536578 Patent Document 5: International Publication No. 2020/110793

[Problems to be Solved by Invention]

When the barrier ribs (partition ribs) are produced using the resist compositions and the like described in Patent Documents 1 to 4, the cured resin product has excellent liquid repellency, but has the following problem: when the above-mentioned UV ozone treatment is performed Or oxygen plasma treatment, the liquid repellency decreased.

An object of the present invention is to provide a fluorine-containing resin capable of producing a barrier rib (partition rib) whose liquid repellency is not easily reduced even if it undergoes UV ozone treatment or oxygen plasma treatment. [Technical means to solve problems]

The inventors of the present invention have made intensive studies in view of the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved by using a monomer having a triple bond in the side chain, and the present invention was completed.

By using the fluorine-containing resin of the present invention, a barrier rib (partition rib) whose liquid repellency is not easily reduced even after UV ozone treatment or oxygen plasma treatment can be produced.

That is, the present invention is as follows.

The fluorine-containing resin of the present invention is characterized by containing, as a monomer unit, a repeating unit (U) containing a monomer (A) having a triple bond in its side chain.

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

It is preferable that the fluorine-containing resin of this invention contains a fluorine atom in the side chain of at least a part of the said monomer (A).

In the fluorine-containing resin of the present invention, at least a part of the triple bond is preferably a carbon-nitrogen triple bond of a nitrile group.

In the fluorine-containing resin of the present invention, at least a part of the above-mentioned monomer (A) preferably has a structure represented by the following formula (1) or formula (1′). CH ₂ =C(R ¹ )C≡CR ² ･･･(1) CH ₂ =C(R ¹ )XC≡CR ² ･･･(1´) (In equations (1) and (1´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, and represents a straight chain with 1 to 10 carbons, a branched chain with 3 to 10 carbons, or a cyclic with 3 to 10 carbons In the alkyl group, any number of hydrogen atoms in the alkyl group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents straight chain with 1 to 15 carbon atoms, and 3 to 15 carbon atoms. branched or cyclic alkyl group with 3 to 15 carbon atoms, any number of hydrogen atoms in the alkyl group can be substituted by fluorine atoms)

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

In the fluorine-containing resin of the present invention, the repeating unit (U) preferably includes the monomer (A) and the monomer (B) having a structure represented by the following formula (3) or formula (3´) as monomer units . CH ₂ =C(R ¹ )COOR ² ･･･(3) CH ₂ =C(R ¹ )COOXR ² ･･･(3´) (In equations (3) and (3´), R ¹ represents hydrogen Atom, fluorine atom, or methyl group; X represents a divalent linking group, and represents a straight chain with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms. , any number of hydrogen atoms in the alkylene can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents a straight chain with 1 to 15 carbons, a branched chain with 3 to 15 carbons or A cyclic alkyl group with 3 to 15 carbon atoms, any number of hydrogen atoms in the alkyl group can be substituted by fluorine atoms)

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

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

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

It is preferable that the photosensitive resin composition of this invention further contains a crosslinking agent and an alkali-soluble resin.

It is preferable to use the photosensitive resin composition of this invention for formation of a partition.

The cured product of the present invention is obtained by curing the above-mentioned photosensitive resin composition of the present invention.

The display of the present invention is characterized by comprising a light-emitting element, and the light-emitting element has: A partition wall comprising the above-mentioned cured product of the present invention; and The light-emitting layer is arranged in the region divided by the partition wall.

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

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

Hereinafter, the present invention will be described in detail, and the description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these specific contents. It can be implemented with various changes within its spirit.

In the column of "Embodiment" in this specification, the matters represented by "[" and "]", "<" and ">" are merely symbols and have no meaning in themselves. In this specification, "polymer" and "resin" are synonymous, and unless otherwise noted, they refer to polymer compounds.

In this specification, "barrier" and "partition" are synonymous, and unless otherwise noted, they refer to the convex portion of the pattern film having concavities and convexities in the ink jet method.

(Fluorine-containing resin) The fluorine-containing resin of the present invention is characterized by containing, as a monomer unit, a repeating unit (U) containing a monomer (A) having a triple bond in its side chain.

By using the fluorine-containing resin of the present invention, a barrier rib (partition rib) having sufficiently high liquid repellency can be produced. Moreover, even if the produced barrier ribs (partitions) are subjected to UV ozone treatment or oxygen plasma treatment, the liquid repellency is not easily reduced. In addition, the reason why the barrier rib (partition rib) with sufficiently high liquid repellency can be produced is estimated as follows. First, it is considered that the liquid repellency improves when the fluorine-containing alkyl group undergoes surface segregation. As will be described later, when the barrier ribs (partition ribs) are produced using the fluorine-containing resin of the present invention, UV ozone treatment or oxygen plasma treatment is performed after the patterned film is formed, and then heat treatment is performed. After using the fluorine-containing resin of the present invention to form a patterned film, by performing UV ozone treatment or oxygen plasma treatment, the π electrons possessed by triple bonds interact with -CH, -OH, -NH bonds, and these functional base is immobilized. On the other hand, a fluorine-containing alkyl group having a weak interaction with the π electron possessed by the triple bond is prone to surface segregation. By heating after that, rearrangement is accelerated|stimulated, and liquid repellency improves.

In this specification, "monomer (A) which has a triple bond in a side chain" means a monomer which has a triple bond at the position which becomes a side chain of a polymer, when a monomer (A) forms a polymer. In this specification, "repeating unit (U)" is a monomeric unit which comprises the main chain of a fluorine-containing resin, and refers to the plural monomeric units which exist in this main chain. Furthermore, the repeating unit (U) may continuously constitute the main chain of the fluororesin, or may constitute the main chain of the fluororesin such that other monomer units exist between the repeating units (U). Moreover, a monomer unit other than a repeating unit (U) may exist in the main chain terminal of a fluorine-containing resin.

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

Furthermore, in this specification, "the content of fluorine atoms in the fluororesin" refers to the molar ratio of the monomers constituting the fluororesin measured by NMR (Nuclear Magnetic Resonance Spectroscopy), the The value calculated from the molecular weight of the monomer and the content of fluorine contained in the monomer. Here, when the fluorine-containing resin is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate The method for measuring the fluorine content will be described. (i) First, the ratio (molar ratio) of each composition is calculated by performing NMR measurement on the fluorine-containing resin. (ii) The molecular weight (Mw) of the monomer of each composition of the fluorine-containing resin is multiplied by the molar ratio, and the obtained values are added to obtain a total value. The weight ratio (wt%) of each composition was calculated from this total value. Furthermore, the molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 1,1-bistrifluoromethylbutadiene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate The molecular weight is 432. (iii) Next, in the composition containing fluorine, the fluorine content rate in the monomer is calculated. (iv) Calculate "fluorine content in monomers/monomer molecular weight (Mw) x weight ratio (wt%)" in each component, and add up the obtained values. (v) Calculate "the value obtained in the above (iv)"/"the total value obtained in the above (ii)", and calculate the content of fluorine atoms in the fluorine-containing resin.

In the fluorine-containing resin of the present invention, at least a part of the monomer (A) preferably has a structure represented by the following formula (1) or formula (1'). CH ₂ =C(R ¹ )C≡CR ² ･･･(1) CH ₂ =C(R ¹ )XC≡CR ² ･･･(1´) (In equations (1) and (1´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, and represents a straight chain with 1 to 10 carbons, a branched chain with 3 to 10 carbons, or a cyclic with 3 to 10 carbons In the alkyl group, any number of hydrogen atoms in the alkyl group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents straight chain with 1 to 15 carbon atoms, and 3 to 15 carbon atoms. branched or cyclic alkyl group with 3 to 15 carbon atoms, any number of hydrogen atoms in the alkyl group can be substituted by fluorine atoms)

Moreover, in the fluorine-containing resin of this invention, it is preferable that the structure represented by said formula (1) or (1') is a structure represented by following formula (2) or formula (2'). CH ₂ =C(R ¹ )C≡CR ^f ･･･(2) CH ₂ =C(R ¹ )XC≡CR ^f ･･･(2´) (In equations (2) and (2´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, and represents a straight chain with 1 to 10 carbons, a branched chain with 3 to 10 carbons, or a cyclic with 3 to 10 carbons In the alkylene group, any number of hydrogen atoms in the alkylene group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ^f represents a straight chain with 1 to 6 carbon atoms, a carbon number of 3 to 6 branched or cyclic perfluoroalkyl with 3 to 6 carbon atoms)

As preferred structures of formula (1) and formula (1´) (including preferred structures of formula (2) and formula (2´)), the following formulae (1-1) to (1-4) can be exemplified and the structures represented by (2-1) to (2-4).

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

Moreover, in the fluorine-containing resin of the present invention, it is preferable that the repeating unit (U) contains the above-mentioned monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3´) as a monomer unit.

CH ₂ =C(R ¹ )COOR ² ･･･(3) CH ₂ =C(R ¹ )COOXR ² ･･･(3´) (In equations (3) and (3´), R ¹ represents hydrogen Atom, fluorine atom, or methyl group; X represents a divalent linking group, and represents a straight chain with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms. , any number of hydrogen atoms in the alkylene can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents a straight chain with 1 to 15 carbons, a branched chain with 3 to 15 carbons or A cyclic alkyl group with 3 to 15 carbon atoms, any number of hydrogen atoms in the alkyl group can be substituted by fluorine atoms)

Moreover, as a monomer represented by formula (3) and formula (3'), it is preferable to have a structure represented by following formula (4) and formula (4').

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

Regarding the formula (4) and the formula (4´), the structures of the following formulae (4´-1) to (4´-3) can be exemplified as more preferable structures.

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

The repeating unit (U) of the fluorine-containing resin of the present invention includes two or more of formula (1), formula (1´), formula (2), formula (2´), formula (3), formula (3´) In the case of different types of structures among the structures represented by the formula (4) and the formula (4´), in each structure, R ¹ , R ² , R ^f and X may be the same or different.

The fluorine-containing resin of the present invention preferably contains a fluorine atom in the side chain of at least a part of the monomer (A). In addition, the fluorine atom may be arranged at a position to become a side chain in the structure represented by the above-mentioned formula (1), formula (1´), formula (2), or formula (2´), or may be arranged in other structures as a side chain position of the chain.

In the fluorine-containing resin of the present invention, at least a part of the triple bond is preferably a carbon-nitrogen triple bond of a nitrile group. In addition, the fluorine atom may be arranged at a position to become a side chain in the structure represented by the above-mentioned formula (1), formula (1´), formula (2), or formula (2´), or may be arranged in other structures as a side chain position of the chain.

The molecular weight of the fluorine-containing resin of the present invention is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more, as a mass average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance 500,000 or less, more preferably 3,000 or more and 100,000 or less. If the molecular weight is less than 1,000, the strength of the formed fluororesin film or organic EL barrier tends to decrease. If the molecular weight is more than 1,000,000, the solubility in the solvent is insufficient, and the formation of the fluororesin film by coating may be possible. will become difficult.

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

The fluorine-containing resin of the present invention can be used for a liquid repellent or a photosensitive resin composition.

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

The photosensitive resin composition of this invention can be used for formation of a barrier rib (partition rib). Since the fluorine-containing resin of the present invention is included, a barrier rib (partition rib) having sufficiently high liquid repellency can be produced. Moreover, even if the produced barrier ribs (partitions) are subjected to UV ozone treatment or oxygen plasma treatment, the liquid repellency is not easily reduced.

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

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

Specific examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol Ethylene 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), Diethylene Glycol Monoethyl Ether Propylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, etc. of dipropylene glycol monoacetate.

As ethers, specifically, diethyl ether, diisopropyl ether, tetrahydrofuran, diethylene, anisole, etc. are mentioned.

Specific examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, and methoxypropionic acid. Methyl ester, ethyl ethoxypropionate, γ-butyrolactone, etc. As an aromatic solvent, xylene, toluene, etc. are mentioned.

As the fluorine-based solvent, chlorofluorocarbons, hydrofluorochlorocarbons, perfluoro compounds, hexafluoroisopropanol, etc. may, for example, be mentioned.

In addition, in order to improve coatability, a turpentine-based naphtha solvent, a paraffin-based solvent, etc., which are high-boiling point weak solvents, can be used.

Wherein, the solvent is preferably at least one selected from the group consisting of the following compounds: methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether , ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether Ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, Dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxypropionate ethyl acetate, gamma-butyrolactone, and hexafluoroisopropanol. More preferably, it is selected from the group consisting of methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone at least one of the group.

The amount of the solvent in the photosensitive resin composition of the present invention is relative to the concentration of the fluorine-containing resin (wherein, when the photosensitive resin composition contains an alkali-soluble resin described later, it is the total concentration including the resin) 100 parts by mass, preferably within a range of 50 parts by mass or more and 2,000 parts by mass or less. More preferably, it is 100 parts by mass or more and 1,000 parts by mass or less. The film thickness of the resin film to be formed can be adjusted by adjusting the amount of the solvent, and when the amount of the solvent is within the above range, the film thickness of the resin film particularly suitable for obtaining a barrier for organic EL can be obtained.

The photopolymerization initiator contained in the photosensitive resin composition of the present invention is not particularly limited as long as it polymerizes a monomer having a polymerizable double bond by high-energy rays such as electromagnetic waves or electron beams, and can be used A well-known photopolymerization initiator. As the photopolymerization initiator, a photoradical initiator or a photoacid initiator may be used, and these may be used alone, a photoradical initiator and a photoacid initiator may be used in combination, or two or more of them may be used together. The light free radical initiator or photoacid initiator is used in combination. In addition, by using an additive together with a photopolymerization initiator, living polymerization can be carried out in some cases, and a known additive can be used as the additive.

Specifically, as photoradical initiators, intramolecular bonds can be classified into intramolecular bond severance types in which radicals are generated by absorbing electromagnetic waves or electron beams; Hydrogen abstraction forms that donate to the body to generate free radicals, etc.; these can be used. Photoradical initiators other than the types exemplified above may also be used.

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

Specific examples of the benzophenone system include: benzophenone, 4-hydroxybenzophenone, 2-benzylbenzoic acid, 4-benzylbenzoic acid, 4,4'-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like. Among them, 2-benzylbenzoic acid, 4-benzylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferable.

Specific examples of acetophenones include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2 '-Dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-𠰌olinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and the like. Among them, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

As a diketone type|system|group, 4,4'- dimethoxybenzyl, methyl benzoate, 9, 10- phenanthrenequinone etc. are mentioned specifically,. Among them, 4,4'-dimethoxybenzyl and methyl benzyl formate are preferable.

As an acyl phosphine oxide system, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide etc. are mentioned specifically,.

As a quinone type, anthraquinone, 2-ethylanthraquinone, camphorquinone, 1, 4- naphthoquinone etc. are mentioned specifically,. Among them, camphorquinone and 1,4-naphthoquinone are preferable.

Specific examples of the alcohol-ketone system include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among them, benzoin and benzoin methyl ether are preferable.

As a photoradical initiator, a benzophenone type, an acetophenone type, and a diketone type are preferable, and a benzophenone type is more preferable.

Among the commercially available light radical initiators, as preferred light radical initiators, there may be exemplified: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, manufactured by BASF Co., Ltd. Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, Lucirin TPO, etc. Among them, Irgacure 651 and Irgacure 369 are more preferable.

鎓、(2,4-環戊二烯-1-基)(1-甲基乙基苯)鐵所組成之群中之至少一種之陽離子、與選自由四氟硼酸鹽、六氟磷酸鹽、六氟銻酸鹽、五氟苯基硼酸鹽所組成之群中之至少一種之陰離子之對之鎓鹽。 其中，尤佳為雙[4-(二苯基鋶基)苯基]硫醚雙六氟磷酸鹽、雙[4-(二苯基鋶基)苯基]硫醚四(五氟苯基)硼酸鹽、二苯基錪六氟磷酸鹽。 Specifically, the photoacid initiator is selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrene, and 9-oxothiol

Onium, at least one cation of the group consisting of (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and a cation selected from tetrafluoroborate, hexafluorophosphate, An onium salt of a pair of anions of at least one of the group consisting of hexafluoroantimonate and pentafluorophenyl borate. Among them, especially preferred are bis[4-(diphenylperyl)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylperyl)phenyl]sulfide tetrakis(pentafluorophenyl) Borate, diphenyl iodonium hexafluorophosphate.

Examples of commercially available photoacid initiators include: product names manufactured by San-Apro Co., Ltd.: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S; Dow Chemical Japan Co., Ltd. Product names manufactured by Co., Ltd.: Cyracure photohardening initiator UVI-6990, Cyracure photohardening initiator UVI-6992, Cyracure photohardening initiator UVI-6976; Product name manufactured by ADEKA Co., Ltd.: Adeka Optomer SP- 150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300; Product names manufactured by Japan Caoda Co., Ltd.: CI-5102, CI-2855; Sanxin Chemical Industry Co., Ltd. Product names manufactured by the company: San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110, San- Aid SI-180; product names manufactured by Lamberti: Esacure 1064, Esacure 1187; product names manufactured by BASF Co., Ltd.: Irgacure 250, etc.

The content of the photopolymerization initiator in the photosensitive resin composition of the present invention relative to the fluorine-containing resin (wherein, when the photosensitive resin composition includes an alkali-soluble resin described later, the total amount including the resin) concentration) 100 parts by mass, preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less. When the content of the photopolymerization initiator is less than 0.1 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and when it exceeds 30 parts by mass, the resolution or sensitivity tends to decrease.

The photosensitive resin composition of the present invention may contain a crosslinking agent, an alkali-soluble resin, a naphthoquinonediazide group-containing compound, a basic compounds, and other additives.

The cross-linking agent contained in the photosensitive resin composition of the present invention reacts with the repeating unit (U) of the fluorine-containing resin, so that the resin can adopt a cross-linked structure, and the mechanical strength of the formed film can be improved.

A known cross-linking agent can be used, and specifically, an amine-containing amine such as formaldehyde or formaldehyde and a lower alcohol and melamine, acetonitrile, benzoguanamine, urea, ethyl urea, propyl urea, and glycoluril can be used. A compound formed by reacting with a base compound, and replacing the hydrogen atom of the amine group with a methylol group or a lower alkoxymethyl group; polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyfunctional isocyanate compounds, polyfunctional Acrylate compounds, etc. Here, the cross-linking agent using melamine is called melamine-based cross-linking agent, the cross-linking agent using urea is called urea-based cross-linking agent, and the cross-linking agent using alkylene urea such as ethyl urea and propylene urea is called Alkylene urea cross-linking agent, the cross-linking agent using glycoluril is called glycoluril-based cross-linking agent. These crosslinking agents may be used alone or in combination of two or more.

The crosslinking agent is preferably at least one selected from these crosslinking agents, and particularly preferably a glycoluril-based crosslinking agent and a polyfunctional acrylate compound.

Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, etc. Among them, hexamethoxymethyl melamine is preferred. methyl melamine.

Examples of the urea-based crosslinking agent include bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, and the like, and among them, bis-methoxymethyl urea is preferred. Methoxymethyl urea.

Examples of the alkylene urea-based crosslinking agent include mono- and/or dimethylol ethyl urea, mono- and/or dimethoxymethyl ethyl urea, mono- and/or diethoxy Ethyl urea-based crosslinking agents such as methylated ethyl urea, mono- and/or dipropoxymethylated ethyl urea, mono- and/or dibutoxymethylated ethyl urea; mono- and/or Dimethylolated propylene urea, mono- and/or dimethoxymethylated propylene urea, mono- and/or diethoxymethylated propyl-propylene urea, mono- and/or dipropoxymethylated Propylene urea, mono- and/or dibutoxymethylated propylene urea and other propylene urea crosslinking agents; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidine ketone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Examples of glycoluril-based crosslinking agents include: mono-, di-, tri-, and/or tetramethylolated glycoluril; mono-, di-, tri-, and/or tetramethoxymethylated glycoluril; , di, tri, and/or tetraethoxymethylated glycoluril; mono, di, tri, and/or tetrapropoxymethylated glycoluril; mono, di, tri, and/or tetrabutoxy Methylated glycoluril, etc.

The polyfunctional acrylate compound may, for example, include polyfunctional acrylates (for example, 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 (for example, product names manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: A-200, A-400, A-600), urethane acrylic acid Esters (for example, product names manufactured by 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), pentaerythritol tetraacrylate, etc.

As the polyfunctional acrylate compound, preferable ones are exemplified below.

[hua 1]

[hua 2]

[hua 3]

The content of the crosslinking agent in the photosensitive resin composition of the present invention is relative to the fluorine-containing resin (wherein, when the photosensitive resin composition contains an alkali-soluble resin described later, it is the total concentration including the resin) 100 parts by mass, preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less. When the content of the crosslinking agent 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 or sensitivity tends to decrease.

When the photosensitive resin composition of this invention contains an alkali-soluble resin, the shape of the barrier rib obtained from the photosensitive resin composition of this invention can be made favorable.

The alkali-soluble resin may, for example, be an alkali-soluble novolak resin. The alkali-soluble novolak resin can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

Specific examples of phenols include: phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol Phenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylphenol Resorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, phloroglucinol , rhizomatol, isogestrel, etc. These phenols may be used alone or in combination of two or more.

Specific examples of aldehydes include formaldehyde, triacetane, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, and o-hydroxybenzaldehyde. , m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, m Benzaldehyde, etc. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, and the like. These acid catalysts may be used alone or in combination of two or more.

Moreover, an acid-modified epoxy acrylate type is mentioned as an alkali-soluble resin. As commercially available acid-modified epoxy acrylates, for example, product names manufactured by Nippon Kayaku Co., Ltd.: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050 can be used , TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H, etc.

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

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

When the photosensitive resin composition of this invention contains a naphthoquinonediazide group containing compound, the shape of the barrier rib obtained from the photosensitive resin composition of this invention can be made favorable. The naphthoquinonediazide group-containing compound is not particularly limited, and a naphthoquinonediazide group-containing compound generally used as a photosensitive component of a resist composition for I-rays can be used.

Specific examples of the naphthoquinone diazide group-containing compound include naphthoquinone-1,2-diazide-4-sulfonate compound, naphthoquinone-1,2-diazide-5- Sulfonate compound, naphthoquinone-1,2-diazide-6-sulfonate compound, naphthoquinone-1,2-diazidesulfonate compound, o-benzoquinonediazidesulfonate compound, o-anthraquinone diazide sulfonate compound, etc. Among them, naphthoquinone-1,2-diazido-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazido-5-sulfonic acid ester compounds, Naphthoquinone-1,2-diazido-6-sulfonate compound. These compounds may be used alone or in combination of two or more.

The content of the naphthoquinonediazide group-containing compound in the photosensitive resin composition of the present invention is relative to the fluorine-containing resin (wherein, when the photosensitive resin composition contains the above-mentioned alkali-soluble resin, the content of the resin is included Total concentration) 100 parts by mass, preferably 10 parts by mass to 60 parts by mass, more preferably 20 parts by mass to 50 parts by mass. When it exceeds 60 weight part, there exists a tendency for it to become difficult to acquire the sensitivity as a photosensitive resin composition.

When the photosensitive resin composition of this invention contains a basic compound, it has the effect|action which slows down the diffusion rate when the acid which the said photoacid generator generate|occur|produces diffuses into the film of the photosensitive resin composition of this invention. By adjusting the basic compound, the acid diffusion distance can be adjusted, and the shape of the barrier can be made good. In addition, by preparing the basic compound, the barrier ribs are not easily deformed even after the formation of the barrier ribs until the exposure time is long, and the barrier ribs with the required accuracy can be stably formed.

As a basic compound, aliphatic amines, aromatic amines, heterocyclic amines, aliphatic polycyclic amines, etc. are mentioned. Among them, aliphatic amines are preferred, and specific examples thereof include secondary or tertiary aliphatic amines, alkyl alcohol amines, and the like. These basic compounds may be used alone or in combination of two or more.

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

Examples of aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, and 2-methylaniline. Aniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-di Nitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine and other aniline derivatives; 1,5-diazabicyclo[4.3.0]nonane -5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dipyridine Heterocyclic amines such as methylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline; bis(1,2,2,6,6-pentamethyl-4-piperidine sebacic acid) base) esters and other hindered amines; 2-hydroxypyridine, aminocresol, 2,4-quinoline diol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine , N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1- Butanol, 4-(2-hydroxyethyl)𠰌line, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperidine, 1-[2-(2-hydroxyethoxy) ) ethyl] piperidine and other alcoholic nitrogen-containing compounds; picoline, lutidine, pyrrole, piperidine, piperidine, indole, hexamethylenetetramine, etc.

In the photosensitive resin composition of the present invention, the content of the basic compound is 100 with respect to the fluorine-containing resin (wherein, when the above-mentioned alkali-soluble resin is included in the photosensitive resin composition, the total concentration including the resin) is 100. The mass part is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass. When the compounding quantity of a basic compound is less than 0.001 mass part, it will become difficult to fully acquire the effect as an additive, and if it exceeds 2 mass parts, there exists a tendency for resolution and sensitivity to fall.

The photosensitive resin composition of this invention may also contain other additives as needed. Examples of other additives include various additives such as dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, levelers, antifoaming agents, compatibilizers, adhesives, and antioxidants. . These other additives may be known additives.

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

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

(1) Film forming step First, after apply|coating the photosensitive resin composition of the said invention to a board|substrate, by heating, the said photosensitive resin composition is made into a fluorine-containing resin film. The heating conditions are not particularly limited, but are preferably performed at 80 to 100° C. for 60 to 200 seconds. Thereby, the solvent etc. contained in the photosensitive resin composition can be removed.

As the substrate, a silicon wafer, metal, glass, ITO (Indium Tin Oxides, indium tin oxide) substrate, etc. can be used. In addition, an organic or inorganic film may be provided on the substrate in advance. For example, it may have an antireflection film, a bottom layer of a multi-layer resist, or a pattern may be formed thereon. In addition, the substrate may be washed in advance. For example, ultrapure water, acetone, alcohol (methanol, ethanol, isopropanol) or the like can be used for washing.

As a method of apply|coating the photosensitive resin composition of this invention to a board|substrate, well-known methods, such as spin coating, can be used.

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

The exposure amount of the high-energy beam 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.

(3) Development step Next, the fluorine-containing resin film after the exposure step is developed with an aqueous alkali solution to prepare a fluorine-containing resin patterned film. That is, a fluorine-containing resin patterned film is produced by dissolving either the exposed portion of the fluorine-containing resin film or the unexposed portion of the film in an aqueous alkaline solution.

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

As a development method, a well-known method can be used, for example, a dipping method, a liquid coating method, a spray method, etc. are mentioned.

The development time (contact time between the developer and the fluororesin film) is preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.

After the development, a step of washing the fluorine-containing resin pattern film with deionized water or the like may also be provided as required. The washing method and washing time are preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.

The partition walls fabricated in this way can be used as barriers for displays.

The display of the present invention is characterized by including a light-emitting element comprising: a partition wall including the photosensitive resin composition of the present invention; and a light-emitting layer disposed in a region divided by the partition wall. As a display, an organic EL display, a quantum dot display, etc. are mentioned. [Example]

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

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

其次，向附帶攪拌機之100 ml玻璃製燒瓶內添加濃硫酸15 g，加溫至100℃，然後歷時1小時緩慢滴加10 g之TFMPO。滴加結束後，於100℃下攪拌60分鐘，藉由 ¹⁹F-NMR對反應液進行解析，結果未檢測到殘留原料。其次，藉由常壓蒸餾，自反應液回收68～70℃之餾份，以55%之產率獲得5,5,5-三氟-2-甲基-1-戊烯-3-炔(以下，記作TFMPY)。 [hua 4]

Next, 15 g of concentrated sulfuric acid was added to a 100 ml glass flask with a stirrer, heated to 100° C., and then 10 g of TFMPO was slowly added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 100° C. for 60 minutes, and the reaction solution was analyzed by ¹⁹ F-NMR. As a result, no residual raw material was detected. Next, by atmospheric distillation, a fraction at 68-70° C. was recovered from the reaction solution to obtain 5,5,5-trifluoro-2-methyl-1-penten-3-yne ( Hereinafter, it is referred to as TFMPY).

[hua 5]

<NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard material: TMS (Tetramethylsilane, tetramethylsilane)); δ(ppm) 1.92 (1H, m) 5.52 (1H, m), 5.85 (1H, m) ¹⁹ F-NMR (solvent: deuterochloroform, standard substance: C ₆ D ₆ ); δ (ppm)-49.8 (3F, S)

[Synthesis Example 2] Synthesis of 4-hydroxystyrene (p-HO-St) (refer to the examples of Japanese Patent Laid-Open No. 2016-98181 for synthesis) At room temperature (about 20°C), in a room with a stirrer In a 1000 ml glass flask, 100 g of 4-acetoxystyrene (a product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St) and 300 g of methanol were mixed, and added as a polymerization inhibitor. 0.50 g of 1,3,5-trihydroxybenzene (corresponding to 0.5 mass % of p-AcO-St). Next, after cooling the solution to 0°C with an ice bath, an aqueous sodium hydroxide solution with a concentration of 12% by mass (equivalent to 1.0 equivalent of p-AcO-St) was slowly added dropwise over 40 minutes, and thereafter, at 0°C Stir for 30 minutes. The reaction liquid was analyzed by ¹ H-NMR, and as a result, no residual raw material was detected. Next, an aqueous hydrochloric acid solution having a concentration of 18% by mass (corresponding to 0.8 equivalent of p-AcO-St) was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes after the completion of the dropwise addition. The pH of the solution was measured and found to be 6. The obtained reaction solution was extracted with 360 g of methyl tert-butyl ether at room temperature (about 20°C). Next, wash twice with 330 g of purified water. 1,3,5-trihydroxybenzene was added to the obtained organic layer so as to correspond to 1% by mass of 4-hydroxystyrene. Then, 4-hydroxystyrene was concentrated to 72 mass %, put into n-octane which was a poor solvent cooled to 0°C, and then immersed the solution in an ice bath and stirred for 1 hour, thereby making 4- Crystallization of hydroxystyrene. The crystals were separated by filtration and washed with n-octane. Next, the crystals were dried at 25°C under reduced pressure to obtain white crystals of 4-hydroxystyrene (hereinafter, referred to as p-HO-St) (yield: 66%).

[hua 6]

2. Production of fluorine-containing resin (first step: polymerization) [Determination of molar ratio of monomers constituting each repeating unit] NMR The molar ratio of monomers constituting each repeating unit in the polymer is determined by ¹ H- The measured value of NMR, ¹⁹ F-NMR, or ¹³ C-NMR was confirmed.

[Determination of molecular weight of polymer] GPC Regarding the weight-average molecular weight Mw and molecular weight dispersion index (ratio of number-average molecular weight Mn to weight-average molecular weight Mw; Mw/Mn) of the polymer, a high-efficiency gel permeation chromatography (hereinafter, sometimes referred to as GPC; Tosoh Corporation) was used. Co., Ltd., model HLC-8320GPC), ALPHA-M column and ALPHA-2500 column (both manufactured by Tosoh Co., Ltd.) were connected in series one by one, and tetrahydrofuran (THF) was used as a developing solvent for measurement. The detector uses a refractive index difference measurement detector.

2-1. Polymerization of fluororesin precursors [Synthesis of fluororesin precursor 1] At room temperature (about 20°C), 10.6 g (0.2 mol) of acrylonitrile (a product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AN), 2-(perfluorobutyl)ethyl methacrylate ( A product of Tokyo Chemical Industry Co., Ltd.; hereinafter, referred to as MA-C4F) 49.8 g (0.15 mol), 2-hydroxyethyl methacrylate (a product of Tokyo Chemical Industry Co., Ltd.; hereinafter, referred to as HEMA) 19.5 g (0.15 mol), and 80 g of methyl ethyl ketone (hereinafter, referred to as MEK) were placed in a 500 ml glass flask with a stirrer, and 2,2'-azobis(2-methylbutyronitrile) ( A product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as AIBN) 1.6 g (0.01 mol), degassed while stirring, and then replaced the flask with nitrogen, heated to an internal temperature of 75°C, and reacted for 6 hours. 400 g of n-heptane was added dropwise to the reaction system, and as a result, a transparent viscous substance was precipitated. The viscous material was isolated by decantation. After drying under reduced pressure at 60°C, 69 g of fluorine-containing resin precursor 1 as a transparent viscous substance was obtained with a yield of 86%.

<NMR measurement results> The composition ratio of the repeating units of the fluorine-containing resin precursor 1 is expressed in mol%, monomer unit derived from AN: monomer unit derived from MA-C4F: monomer unit derived from HEMA=41:28:31.

含氟樹脂前驅物1 [hua 7]

Fluorine-containing resin precursor 1

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

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

<NMR measurement results> The composition ratio of each repeating unit of the fluororesin precursor 2 is expressed in mol%, monomer unit derived from AN: monomer unit derived from MA-C6F: monomer unit derived from HEMA=42:27:31 .

含氟樹脂前驅物2 [hua 8]

Fluorine resin precursor 2

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

[Synthesis of fluororesin precursor 3] Except for using methacrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter, referred to as MN) instead of AN, in the same procedure as the synthesis of fluorine-containing resin precursor 1, a yield of 83% was obtained including the following repetitions Fluorine-containing resin precursor 3 of the unit.

<NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 3 is expressed in mol%, monomer unit derived from MN: monomer unit derived from MA-C4F: monomer unit derived from HEMA=40:28:32 .

含氟樹脂前驅物3 [Chemical 9]

Fluorine resin precursor 3

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

[Synthesis of fluororesin precursor 4] In the same sequence as the synthesis of fluororesin precursor 2, except that MN was used in place of AN, fluororesin precursor 4 comprising the following repeating units was obtained in a yield of 83%.

<NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 4 is expressed in mol%, monomer unit derived from MN: monomer unit derived from MA-C6F: monomer unit derived from HEMA=39:29:32 .

含氟樹脂前驅物4 [Chemical 10]

Fluorine resin precursor 4

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

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

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

含氟樹脂前驅物5 [Chemical 11]

Fluorine resin precursor 5

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

[Synthesis of fluororesin precursor 6] In the same procedure as in the synthesis of fluororesin precursor 2, except that TFMPY obtained in Synthesis Example 1 was used instead of AN, fluororesin precursor 6 containing the following repeating units was obtained with a yield of 81%.

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

含氟樹脂前驅物6 [Chemical 12]

Fluorine resin precursor 6

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

[Synthesis of fluororesin precursor 7] At room temperature (about 20°C), take 10.6 g (0.2 mol) of AN, 49.8 g (0.15 mol) of MA-C4F, 19.5 g (0.15 mol) of HEMA, and 8.66 g (0.1 mol) of methacrylic acid (hereinafter, referred to as MAA), and 89 g of MEK were placed in a 500 ml glass flask with a stirrer, 1.6 g (0.01 mol) of AIBN was added, and the flask was degassed while stirring, and then the flask was replaced with nitrogen. , the temperature was raised to an internal temperature of 75°C, and the reaction was carried out for 6 hours. 450 g of n-heptane was added dropwise to the reaction system, and as a result, a transparent viscous substance was precipitated. The viscous material was isolated by decantation. After drying under reduced pressure at 60°C, 74 g of fluorine-containing resin precursor 7 as a transparent viscous substance was obtained with a yield of 84%.

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

含氟樹脂前驅物7 [Chemical 13]

Fluorine resin precursor 7

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

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

<NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 8 is expressed in mol%, the monomer unit derived from MN: the monomer unit derived from MA-C6F: the monomer unit derived from HEMA: the monomer derived from MAA Volume unit = 34:23:25:18.

含氟樹脂前驅物8 [Chemical 14]

Fluorine resin precursor 8

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

[Synthesis of fluororesin precursor 9] In the same procedure as the synthesis of fluorine-containing resin precursor 7, except that MA-C6F was used instead of MA-C4F and acrylic acid (hereinafter, referred to as AA) was used instead of MAA, a compound containing the following repeating units was obtained in 81% yield. Fluorine resin precursor 9.

<NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 9 is expressed in mol%, the monomer unit derived from AN: the monomer unit derived from MA-C6F: the monomer unit derived from HEMA: the monomer derived from AA Volume unit = 34:23:27:16.

含氟樹脂前驅物9 [Chemical 15]

Fluorine resin precursor 9

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

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

<NMR measurement results> The composition ratio of each repeating unit of the fluorine-containing resin precursor 10 is expressed in mol%, the monomer unit derived from MN: the monomer unit derived from MA-C4F: the monomer unit derived from HEMA: the monomer unit derived from AA Volume unit = 33:24:26:17.

含氟樹脂前驅物10 [Chemical 16]

Fluorine resin precursor 10

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

2-2. Comparative Synthesis of Fluorine Resin Precursors [Comparative Polymerization Example 1] At room temperature (about 20°C), 43.2 g (0.1 mol) of MA-C6F and 23.6 g (0.1 mol) of hexafluoroisopropyl methacrylate (manufactured by Central Glass Co., Ltd., hereinafter referred to as HFIP) were taken. -M), 17.32 g (0.2 mol) of MAA, 84 g of MEK, and 1.6 g (0.010 mol) of AIBN were placed in a 300 ml glass flask with a stirrer, degassed while stirring, and then the flask was The interior was replaced with nitrogen, and the temperature was raised to 80°C, followed by a reaction for 6 hours. The reaction after the completion of the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. The precipitate was separated by filtration and dried under reduced pressure at a temperature of 60° C. to obtain 55 g of Comparative Fluorine-Containing Resin Precursor 1 as a white solid in a yield of 64%.

<NMR measurement results> The composition ratio of each repeating unit of the comparative fluororesin precursor 1 is expressed in molar ratio, monomer unit derived from MA-C6F: monomer unit derived from HFIP-M: monomer unit derived from MAA=26: 20:54.

比較含氟樹脂前驅物1 [Chemical 17]

Comparison of fluororesin precursors 1

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

[Comparative Polymerization Example 2] At room temperature, 13.01 g (0.1 mol) of HEMA, 43.2 g (0.1 mol) of MA-C6F, 23.6 g (0.1 mol) of HFIP-M, 8.66 g (0.1 mol) of MAA, and 88 g of The MEK was placed in a 300 ml glass flask with a stirrer, 1.6 g (0.010 mol) of AIBN was added, and the mixture was degassed while stirring. The flask was then replaced with nitrogen, and the temperature was raised to 80°C, followed by a reaction for 6 hours. The reaction after the completion of the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. The precipitate was separated by filtration, and dried under reduced pressure at a temperature of 60° C. to obtain 60 g of comparative fluororesin precursor 2 as a white solid in a yield of 68%.

<NMR measurement results> The composition ratio of each repeating unit of the comparative fluororesin precursor 2 is expressed in molar ratio, monomer unit derived from HEMA: monomer unit derived from MA-C6F: monomer unit derived from HFIP-M: derived from Monomer units of MAA = 24:26:24:26.

比較含氟樹脂前驅物2 [Chemical 18]

Comparison of fluororesin precursors 2

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

[Comparative Polymerization Example 3] At room temperature, 12.2 g (0.10 mol) of p-HO-St obtained in Synthesis Example 2, 43.2 g (0.1 mol) of MA-C6F, and 8.8 g (0.1 mol) of 2-hydroxyethyl vinyl ether ( A product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as HEVE), and 64 g of MEK were placed in a 300 ml glass flask with a stirrer, and 1.6 g (0.010 mol) of AIBN was added, and degassed while stirring. , and the inside of the flask was replaced with nitrogen gas, and the temperature was raised to 80° C., and then reacted for 6 hours. The reaction after the completion of the reaction was dropped into 500 g of n-heptane to obtain a white precipitate. The precipitate was separated by filtration, and dried under reduced pressure at a temperature of 60° C. to obtain 51 g of the comparative fluororesin precursor 3 as a white solid in a yield of 81%.

<NMR measurement results> The composition ratio of each repeating unit of the comparative fluororesin precursor 3 is expressed in molar ratio, monomer unit derived from HEVE: monomer unit derived from MA-C6F: monomer unit derived from p-HO-St= 35:31:34.

比較含氟樹脂前驅物3 [Chemical 19]

Comparison of fluororesin precursors 3

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

3. Manufacture of fluorine-containing resin (second step: addition reaction) Fluorine-containing resin precursors 1 to 6 and comparative fluorine-containing resin precursors 1 to 3 obtained in "2. Production of fluorine-containing resin (first step: polymerization)" were reacted with acrylic derivatives to synthesize Fluorine resin. As the acrylic acid derivative, Karenz-AOI (product of Showa Denko Co., Ltd.) was used. The reaction is an addition reaction between the hydroxyl group in each fluorine-containing resin precursor and the acrylic acid derivative.

Karenz-AOI [hua 20]

Karenz-AOI

[Synthesis of Fluorine Resin 1] Take 10 g (hydroxyl equivalent of 0.019 mol) of the fluororesin precursor 1, 20 g of PGMEA and put them in a 300 ml glass flask with a stirrer, add 2.68 g (0.019 mol) of Karenz-AOI, at 45 ° C The reaction was carried out for 4 hours. After the reaction liquid after the completion of the reaction was concentrated, 150 g of n-heptane was added to precipitate a precipitate. The precipitate was separated by filtration, and dried under reduced pressure at 40° C. to obtain 11.4 g of Fluorine-containing Resin 1 as a white solid in a yield of 90%.

< ¹³ C-NMR measurement results> In the fluorine-containing resin 1, the introduction amount (reaction rate) and the residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 1 were 96:4 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from AN, monomer unit derived from MA-C4F) that did not react with the crosslinking group site was compared with that of the fluororesin precursor 1 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 2] Fluorine-containing resin 2 was obtained with a yield of 91% in the same procedure as in the synthesis of fluorine-containing resin 1, except that fluorine-containing resin precursor 2 was used instead of fluorine-containing resin precursor 1.

< ¹³ C-NMR measurement results> In the fluorine-containing resin 2, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 2 were 95:5 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from AN, monomer unit derived from MA-C6F) that did not react with the crosslinking group site was compared with the fluororesin precursor 2 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 3] Fluorine-containing resin 3 was obtained with a yield of 90% in the same procedure as the synthesis of fluorine-containing resin 1 except that fluorine-containing resin precursor 3 was used instead of fluorine-containing resin precursor 1 .

< ¹³ C-NMR measurement results> In the fluorine-containing resin 3, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in the fluorine-containing resin 3 were 97:3 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C4F) that did not react with the crosslinking group site was compared with that of the fluororesin precursor 3 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 4] Fluorine-containing resin 4 was obtained with a yield of 89% in the same procedure as the synthesis of fluorine-containing resin 1, except that fluorine-containing resin precursor 4 was used instead of fluorine-containing resin precursor 1.

< ¹³ C-NMR measurement results> In fluorine-containing resin 4, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 4 were 96:4 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C6F) that did not react with the crosslinking group site was compared with the fluororesin precursor 4 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 5] Fluorine-containing resin 5 was obtained with a yield of 92% in the same procedure as the synthesis of fluorine-containing resin 1 except that fluorine-containing resin precursor 5 was used instead of fluorine-containing resin precursor 1 .

< ¹³ C-NMR measurement results> In fluorine-containing resin 5, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 5 were 95:5 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from TFMPY, monomer unit derived from MA-C4F) that did not react with the crosslinking group site was compared with the fluororesin precursor 5 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 6] Fluorine-containing resin 6 was obtained with a yield of 89% in the same procedure as the synthesis of fluorine-containing resin 1 except that fluorine-containing resin precursor 6 was used instead of fluorine-containing resin precursor 1 .

< ¹³ C-NMR measurement results> In the fluorine-containing resin 6, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 6 were 96:4 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from TFMPY, monomer unit derived from MA-C6F) that did not react with the crosslinking group site was compared with that of the fluororesin precursor 6 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 7] Take 10 g of fluorine-containing resin precursor 7 (alcohol hydroxyl equivalent of 0.018 mol) and 20 g of PGMEA and put them in a 300 ml glass flask with a stirrer, add 2.52 g (0.018 mol) of Karenz-AOI, at 45 ° C The reaction was continued for 5 hours. After the reaction liquid after the completion of the reaction was concentrated, 150 g of n-heptane was added to precipitate a precipitate. The precipitate was separated by filtration, and dried under reduced pressure at 40° C. to obtain 12.0 g of fluorine-containing resin 7 as a white solid in a yield of 96%.

< ¹³ C-NMR measurement results> In fluorine-containing resin 7, the introduction amount (reaction rate) and residual alcoholic hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 7 were 96 in molar ratio :4. In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from AN, monomer unit derived from MA-C4F) that did not react with the crosslinking group site was compared with that of the fluororesin precursor 7 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 8] The fluororesin 8 was obtained with a yield of 93% in the same procedure as in the synthesis of the fluororesin 7 except that the fluororesin precursor 8 was used instead of the fluororesin precursor 7 .

< ¹³ C-NMR measurement results> In the fluorine-containing resin 8, the introduction amount (reaction rate) and the residual alcoholic hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in the fluorine-containing resin 8 were 97 in molar ratio :3. In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C6F) that did not react with the crosslinking group site was compared with that of the fluorine-containing resin precursor 8 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine-containing Resin 9] The fluorine-containing resin 9 was obtained with a yield of 90% in the same procedure as the synthesis of the fluorine-containing resin 7 except that the fluorine-containing resin precursor 9 was used instead of the fluorine-containing resin precursor 7 .

< ¹³ C-NMR measurement results> In fluorine-containing resin 9, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI in fluorine-containing resin 9 were 95:5 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from AN, monomer unit derived from MA-C6F) that did not react with the crosslinking group site was compared with that of the fluorine-containing resin precursor 9 used. No change (same as before the introduction of the crosslinking group).

[Synthesis of Fluorine Resin 10] The fluororesin 10 was obtained with a yield of 93% in the same procedure as in the synthesis of the fluororesin 7 except that the fluororesin precursor 10 was used instead of the fluororesin precursor 7 .

< ¹³ C-NMR measurement results> In the fluorine-containing resin 10 , the introduction amount (reaction rate) and the residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI were 96:4 in molar ratio . In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MN, monomer unit derived from MA-C4F) that did not react with the crosslinking group site was compared with that of the fluororesin precursor 10 used. No change (same as before the introduction of the crosslinking group).

[Comparative synthesis of fluororesin 1] Comparative fluororesin 1 was obtained with a yield of 89% in the same procedure as in the synthesis of fluororesin 1, except that comparative fluororesin precursor 1 was used instead of fluororesin precursor 1.

< ¹³ C-NMR measurement results> In Comparative Fluorine-containing Resin 1, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI were 96 in molar ratio: 4. In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MA-C6F, monomer unit derived from HFIP-M) that did not react with the crosslinking group site was compared with the fluorine-containing resin precursor used No change compared to 1 (same as before the introduction of the cross-linking group).

[Comparative synthesis of fluororesin 2] Comparative fluororesin 2 was obtained with a yield of 90% in the same procedure as in the synthesis of fluororesin 1, except that comparative fluororesin precursor 2 was used instead of fluororesin precursor 1.

< ¹³ C-NMR measurement results> In the comparative fluororesin 2, the introduction amount (reaction rate) and the residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI were 96 in molar ratio: 4. In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MA-C6F, monomer unit derived from HFIP-M) that did not react with the crosslinking group site was compared with the used fluorine-containing resin precursor 2 There is no change compared to that (same as before the introduction of the cross-linking group).

[Comparative synthesis of fluororesin 3] Comparative fluororesin 3 was obtained with a yield of 90% in the same procedure as in the synthesis of fluororesin 1, except that comparative fluororesin precursor 3 was used in place of fluororesin precursor 1.

< ¹³ C-NMR measurement results> In Comparative Fluorine-containing Resin 3, the introduction amount (reaction rate) and residual hydroxyl group amount (unreacted rate) of the acrylic derivative derived from Karenz-AOI were 95 in molar ratio: 5. In addition, it was confirmed that the composition ratio of each repeating unit (monomer unit derived from MA-C6F) that did not react with the cross-linking group site did not change compared with the comparative fluororesin precursor 3 used (compared with the introduction of cross-linking group). The same as before the base).

4. Preparation of photosensitive resin composition [Preparation of Photosensitive Resin Composition 1] 0.5 parts by mass of the manufactured fluorine-containing resin 1, 0.5 parts by mass of Irgacure 369 (product of BASF Co., Ltd.) as a photopolymerization initiator, and 50 parts by mass of pentaerythritol tetraacrylate (Tokyo) as a crosslinking agent were prepared. A product of Kasei Industry Co., Ltd.), 50 parts by mass of alkali-soluble resin ZAR2051H (a product of Nippon Kayaku Co., Ltd.), 160 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 70 parts by mass as a solvent A photosensitive resin composition 1 was prepared by filtering the obtained solution with a 0.2 μm membrane filter using parts by mass of propylene glycol monomethyl ether (PGME).

[Preparation of Photosensitive Resin Composition 2] Photosensitive resin composition 2 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 2 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 3] Photosensitive resin composition 3 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 3 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 4] Photosensitive resin composition 4 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 4 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 5] Photosensitive resin composition 5 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 5 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 6] Photosensitive resin composition 6 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 6 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 7] Photosensitive resin composition 7 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 7 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 8] Photosensitive resin composition 8 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 8 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 9] Photosensitive resin composition 9 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that fluorine-containing resin 9 was used instead of fluorine-containing resin 1 .

[Preparation of Photosensitive Resin Composition 10] The photosensitive resin composition 10 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluorine-containing resin 10 was used instead of the fluorine-containing resin 1 .

[Preparation of Comparative Photosensitive Resin Composition 1] Comparative photosensitive resin composition 1 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that comparative fluororesin 1 was used instead of fluororesin 1.

[Preparation of Comparative Photosensitive Resin Composition 2] Comparative photosensitive resin composition 2 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that comparative fluororesin 2 was used in place of fluororesin 1.

[Preparation of Comparative Photosensitive Resin Composition 3] Comparative photosensitive resin composition 3 was prepared in the same procedure as the preparation of photosensitive resin composition 1 except that comparative fluororesin 3 was used instead of fluororesin 1.

5. Evaluation of the barrier Using photosensitive resin compositions 1 to 10 and comparative photosensitive resin compositions 1 to 3 obtained in "4. Preparation of photosensitive resin compositions", barrier ribs 1 to 10 and comparative barrier ribs 1 to 3 were formed. Evaluate and compare. Table 1 shows the results of the barrier ribs of the present invention and the results of the comparative barrier ribs.

[Barrier formation] A 10 cm square ITO substrate was washed with ultrapure water and then with acetone, and then the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment apparatus (manufactured by SEN Special Light Source Co., Ltd., model: PL17-110). Next, using the photosensitive resin compositions 1 to 10 and comparative photosensitive resin compositions 1 to 3 obtained in "4. Preparation of the photosensitive resin composition", the photosensitive resin compositions 1 to 3 were coated with a spin coater at a rotational speed of 1,000 rpm. The obtained substrate after UV ozone treatment was heated on a hot plate at 100° C. for 150 seconds to form a fluororesin film with a film thickness of 2 μm and a comparative fluororesin film. Using a mask alignment exposure machine (manufactured by SUSS MicroTec Co., Ltd.), the obtained resin film was irradiated with i-rays (wavelength: 365 nm) through a mask with a line and gap of 5 μm to perform exposure. About the obtained resin film after exposure, the developer solution solubility, the evaluation of barrier property (sensitivity, resolution), and the measurement of the contact angle were performed.

[Developer Solubility] The exposed resin film on the ITO substrate was immersed in an alkaline developing solution at room temperature for 80 seconds, and the solubility in the alkaline developing solution was evaluated. As an alkali developing solution, a 2.38 mass % tetramethylammonium hydroxide aqueous solution (hereinafter, sometimes referred to as TMAH) was used. The solubility of the barrier ribs was evaluated by measuring the film thickness of the barrier ribs after immersion using a contact film thickness meter. The case where the barrier was completely dissolved was referred to as "soluble", and the case where the barrier remained undissolved was referred to as "insoluble". The results are shown in Table 1.

[Barrier performance (sensitivity, resolution)] The optimum exposure amount Eop (mJ/cm ² ) at the time of forming the above-mentioned pattern of lines and spaces, that is, the barrier ribs, was obtained and used as an index of sensitivity. Moreover, the obtained barrier rib pattern was observed with a microscope, and the resolution was evaluated. Those who could not confirm the line edge roughness were set as "excellent", those who were slightly confirmed were set as "good", and those which were obvious were set as "failure". The results are shown in Table 1.

[Table 1] barrier 1 2 3 4 5 6 7 8 9 10 Compare 1 Compare 2 Compare 3 Photosensitive resin composition 1 2 3 4 5 6 7 8 9 10 Compare 1 Compare 2 Compare 3 Developer Solubility unexposed part Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Soluble Exposure Department insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble insoluble Barrier performance Sensitivity (mJ/cm ² ) 102 105 102 102 100 102 100 102 102 102 105 102 100 Resolution excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent

[Contact angle] After heating the substrate with barrier ribs obtained by the above steps at 230° C. for 60 minutes, UV ozone treatment or oxygen plasma treatment was performed on the entire surface of the substrate for 10 minutes. Then, it heated at 230 degreeC for 60 second. Before and after the UV ozone treatment or oxygen plasma treatment, and after the heating step, the contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: DMs-601) was used to measure the values of each barrier surface for anisole, PGMEA, and the contact angle of water. The results are shown in Table 2. Furthermore, the UV ozone treatment device used is the same as the above-mentioned UV ozone treatment device. Moreover, as an oxygen plasma processing apparatus, the plasma dry cleaning machine PDC210 by Yamato Scientific Co., Ltd. was used, and oxygen plasma processing was performed under the conditions of an oxygen flow rate of 30 cc/min and an output of 300 W.

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

As shown in Table 1, the barrier ribs of the present invention and the comparative barrier ribs are both negative-type resists in which only the unexposed part dissolves in the evaluation of the solubility of the developer solution, and show the same degree of sensitivity in the evaluation of the barrier rib performance. The 5 μm lines and gaps were transferred with better resolution, and the resolution of the roughness of the line edge was not observed to be “excellent”. That is, based on these evaluations, it can be seen that the fluorine-containing resin of the present invention and the comparative fluorine-containing resin have less influence on the barrier ribs.

On the other hand, as shown in Table 2, in the barrier ribs of the present invention, the contact angles of the exposed portion (corresponding to the upper surface of the barrier ribs) with respect to anisole, PGMEA, and water are reduced by UV ozone treatment or oxygen plasma treatment. It decreased, but increased by the subsequent heating step, thus showing good liquid repellency. In the comparative barrier ribs, the contact angle was decreased due to UV ozone treatment or oxygen plasma treatment, and the contact angle remained low with little change even by the subsequent heating step.

Claims (15)

A fluorine-containing resin characterized by containing a repeating unit (U) comprising a monomer (A) having a triple bond in the side chain as a monomer unit. The fluorine-containing resin according to claim 1 has a fluorine atom content of 5% by mass or more. The fluorine-containing resin according to claim 1 or 2, wherein at least a part of the side chain of the above-mentioned monomer (A) contains a fluorine atom. The fluorine-containing resin according to any one of claims 1 to 3, wherein at least a part of the triple bond is a carbon-nitrogen triple bond of a nitrile group. The fluorine-containing resin according to any one of claims 1 to 4, wherein at least a part of the above-mentioned monomer (A) has a structure represented by the following formula (1) or formula (1´): CH ₂ =C(R ¹ )C≡CR ² ･･･(1) CH ₂ =C(R ¹ )XC≡CR ² ･･･(1´) (In formulas (1) and (1´), R ¹ represents a hydrogen atom, fluorine Atom, or methyl group; X represents a divalent linking group, represents a straight chain with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic alkyl group with 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkyl group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents straight chain with 1-15 carbons, branched with 3-15 carbons or 3 carbons A cyclic alkyl group of ~15, any number of hydrogen atoms in the alkyl group may be substituted with fluorine atoms). The fluorine-containing resin according to claim 5, wherein the structure represented by the above formula (1) or (1´) is a structure represented by the following formula (2) or formula (2´): CH ₂ =C(R ¹ ) C≡CR ^f ･･･(2) CH ₂ =C(R ¹ )XC≡CR ^f ･･･(2´) (In formula (2) and formula (2´), R ¹ represents a hydrogen atom or a fluorine atom , or methyl; X represents a divalent linking group, represents a straight chain with 1 to 10 carbons, a branched chain with 3 to 10 carbons or a cyclic alkylene with 3 to 10 carbons, the alkylene Any number of hydrogen atoms in the group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ^f represents straight chain with 1-6 carbons, branched with 3-6 carbons or carbon number 3- The cyclic perfluoroalkyl group of 6). The fluorine-containing resin according to any one of claims 1 to 6, wherein the repeating unit (U) comprises the monomer (A) and the monomer having the structure represented by the following formula (3) or formula (3´) (B) As a monomer unit: CH ₂ =C(R ¹ )COOR ² ･･･(3) CH ₂ =C(R ¹ )COOXR ² ･･･(3´) (Equations (3) and (3) ´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, which represents a straight chain with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a branched chain with 3 to 10 carbon atoms. A cyclic alkylene group of 10, any number of hydrogen atoms in the alkylene group can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ² represents a straight chain with carbon number 1-15, carbon number 3-15 branched or cyclic alkyl groups with 3-15 carbon atoms, any number of hydrogen atoms in the alkyl group can be substituted by fluorine atoms). The fluorine-containing resin according to claim 7, wherein the structure represented by the above formula (3) or formula (3´) is the structure represented by the following formula (4) or formula (4´): CH ₂ =C(R ¹ )COOR ^f ･･･(4) CH ₂ =C(R ¹ )COOXR ^f ･･･(4´) (In formulas (4) and (4´), R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group; X represents a divalent linking group, which represents a straight chain with 1 to 10 carbons, a branched chain with 3 to 10 carbons, or a cyclic alkylene with 3 to 10 carbons. Any number of hydrogen atoms can be substituted by hydroxyl or -OC(=O)-CH ₃ ; R ^f represents straight chain with 1-6 carbons, branched with 3-6 carbons or ring with 3-6 carbons as perfluoroalkyl). A liquid repellent comprising the fluorine-containing resin according to any one of claims 1 to 8. A photosensitive resin composition characterized by comprising at least the fluorine-containing resin according to any one of claims 1 to 8, a solvent, and a photopolymerization initiator. The photosensitive resin composition according to claim 10, further comprising a crosslinking agent and an alkali-soluble resin. The photosensitive resin composition according to claim 10 or 11, which is used for forming partition walls. A cured product, characterized in that it is obtained by curing the photosensitive resin composition according to any one of claims 10 to 12. A display characterized by comprising a light-emitting element, the light-emitting element having: a partition wall comprising the hardened material as claimed in claim 13; and The light-emitting layer is arranged in the region divided by the partition wall. The display of claim 14, which is an organic EL display or a quantum dot display.