Fluorine-based resin and method for forming patterns using the same

Abstract

To provide a fluorine-based resin as a pattern forming material that has no reduction in liquid repellency on the outside of the pattern and has no reduction in liquid lyophilicity on the inside of the pattern, and to provide a method for forming pattern using the same.SOLUTION: Provided is a fluorine-based resin that has a repeating unit represented by the following formula (1) containing a photocrosslinkable group and a repeating unit containing fluorine atom by 20 mol% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a fluororesin and a method for forming a pattern using the same. [Background technology]

[0002] In recent years, there has been active technological development regarding the manufacture of organic electronic devices using a low-cost, highly productive all-printing method. For example, the development of organic transistors is progressing. These organic transistors are manufactured through numerous processes, including a step where a protective film made of resin protects the organic transistor and a step in forming the electroluminescent (EL) light-emitting pattern. This pattern is, for example, provided to cover the source electrode, drain electrode, and organic semiconductor or polymer layer, and is not present on the electrodes where the EL light-emitting portion is formed.

[0003] Typically, the EL light-emitting portion is formed using photolithography, a technique that involves exposing a substrate surface coated with a photosensitive material (resist) to a pattern via a photomask or reticle, thereby forming a pattern consisting of exposed and unexposed areas. In photolithography, the EL light-emitting portion is opened up by either dry etching or wet etching.

[0004] Photoreactive polymer materials are used as pattern-forming materials. In coating methods such as all-printing, the material is dissolved in a solvent to form an ink, which is then applied. After the solvent is dried and removed, the material is photocrosslinked to make it insoluble in the solvent and form a pattern. Therefore, polymer materials used in coating methods such as all-printing are required to have excellent solubility in the solvent and to be able to undergo photocrosslinking at room temperature and with short exposure time after solvent removal.

[0005] Here, we describe a method for manufacturing organic electroluminescent elements included in organic electroluminescent displays and organic electroluminescent lighting. First, the polymer material is applied to a substrate, and the areas where a pattern is to be formed are photocrosslinked, while the areas that have not been photocrosslinked are removed. The remaining areas then form the pattern. Various functional layers are then laminated onto the areas where the polymer material has been removed (hereinafter referred to as the "inside of the pattern"). While a technique using ink-like raw materials to form these functional layers is promising, the materials constituting the pattern are expected to have liquid-repellent properties from the viewpoint of preventing ink adhesion into the inside of the pattern and preventing ink leakage beyond the areas where the polymer material has not been removed (hereinafter referred to as the "outside of the pattern").

[0006] Examples of such materials include methods for forming patterns using fluororesins or compositions described in Patent Document 1 and Non-Patent Document 1. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2011-184517 [Non-patent literature]

[0008] [Non-Patent Document 1] J Polym Sci A Polym Chem 53, 1252(2015) [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, when processing with a UV ozone cleaner or plasma cleaner as a dry process to improve the hydrophilicity inside the pattern and reduce contact resistance, there is a problem in that the ashing residue of the fluororesin causes a decrease in the liquid repellency outside the pattern and a decrease in the hydrophilicity inside the pattern.

[0010] The present invention has been made in view of the above problems, and its objective is to provide a fluororesin, which is a pattern-forming material that does not reduce the liquid repellency outside the pattern and does not reduce the hydrophilicity inside the pattern, and a method for forming a pattern using the same. [Means for solving the problem]

[0011] As a result of diligent research to solve the above problems, the present inventors have found that a specific fluororesin and a pattern forming method including a cleaning process can solve the above problems, and have completed the present invention.

[0012] In other words, the present invention relates to a method for forming a pattern, characterized by obtaining a photocrosslinked product using a fluororesin having specific repeating units containing photocrosslinkable groups and repeating units containing 20 mol% or more of fluorine atoms, and a substrate, using a composition containing the fluororesin and at least one of an organic solvent and a fluorine solvent, forming a pattern, performing a dry process, and then further washing with an alkaline solution and / or alcohol.

[0013] In other words, the present invention has the following gist. [1] A fluororesin having repeating units represented by the following formula (1) containing a photocrosslinkable group, and repeating units containing 20 mol% or more of fluorine atoms.

[0014] [ka]

[0015] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, A represents an m-valent linking group, R2, R3, R4, R5 and R6 are the same or different and each represents one member selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 3 or more, and n represents an integer of m - 1.) [2] The fluororesin according to [1], wherein the repeating unit containing a fluorine atom is a repeating unit represented by the following formula (2).

[0016]

Chemical formula

[0017] (In formula (2), R7 represents a hydrogen atom or a methyl group. L2 represents a single bond or a divalent linking group, and Rf1 represents one member selected from the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, and a cyclic fluoroalkyl group having 3 to 15 carbon atoms.) [3] A composition comprising the fluororesin according to [1] or [2] and at least one of an organic solvent and a fluorine-based solvent. [4] A photocrosslinked product of the composition according to [3]. [5] A pattern composed of the photocrosslinked product according to [4]. [6] An electronic device comprising the photocrosslinked product according to [4]. [7] A method for forming a pattern, comprising obtaining a photocrosslinked product by using the composition according to [3] on a substrate, forming a pattern, performing a dry process, and then further washing with an alkaline solution and / or alcohol. [8] The method for forming a pattern according to [7], wherein the alkaline solution is an aqueous solution of an alkali containing at least one of inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, and cyclic amines. [9] A method for forming the pattern described in [7], wherein the alcohol is a saturated aliphatic alcohol having 1 to 4 carbon atoms.

[10] A method for forming a pattern according to any one of the following [7] to [9], wherein the dry process is a dry process using at least one of a plasma device, a UV ozone device, and a reactive ion etching device. [Effects of the Invention]

[0018] The fluororesin of the present invention is a pattern-forming material that exhibits excellent liquid repellency outside the pattern and excellent hydrophilicity inside the pattern. By using a composition containing the fluororesin and at least one of an organic solvent and a fluororesin, a pattern-forming method can be provided that can form a pattern that exhibits excellent liquid repellency outside the pattern and excellent hydrophilicity inside the pattern. [Brief explanation of the drawing]

[0019] [Figure 1] This is a diagram showing the cross-sectional shape of an organic transistor. [Figure 2] This is a diagram showing the cross-sectional shape of an organic transistor, which is one form of the electronic device of the present invention. [Figure 3] This figure shows the 1H-NMR chart of fluororesin 1 produced in Example 1. [Modes for carrying out the invention]

[0020] The fluororesin of the present invention is a fluororesin having repeating units represented by the following formula (1) that include a photocrosslinkable group, and repeating units that include 20 mol% or more of fluorine atoms.

[0021] [ka]

[0022] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, A represents an m-valent linking group, and R2, R3, R4, R5, and R6 are the same or different, and represent one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear alkyl halide having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 3 or more, and n represents an integer of m-1.) In the above-mentioned fluororesin, formula (1) has a photocrosslinkable group. By having a photocrosslinkable group, the fluororesin exhibits high photoreactivity, making it possible to selectively insolubilize only the areas irradiated with light in a film obtained by coating the resin.

[0023] In formula (1), R1 represents a hydrogen atom or a methyl group.

[0024] In formula (1), L1 represents a single bond or a divalent linking group.

[0025] The divalent linking group in L1 is preferably a divalent linking group that combines at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-). This makes it possible to form a flat and crack-free film.

[0026] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0027] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-tylpropylene group.

[0028] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0029] Examples of arylene groups having 6 to 12 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0030] Of these divalent linking groups, it is more preferable that they are ester bonds (-C(=O)O-) formed by combining a carbonyl group and an ether group, or linking groups formed by combining a phenylene group and an ether group, and even more preferable that they are (-C(=O)O-).

[0031] In equation (1), A represents an m-valent linking group.

[0032] m represents an integer greater than or equal to 3, preferably an integer between 3 and 5, more preferably an integer between 3 and 4, and even more preferably 3.

[0033] A may be a C1-C24 hydrocarbon group with an m-valent value, which may have substituents, as it improves the solubility of the resulting resin in organic solvents and fluorinated solvents.

[0034] Examples of substituents that the m-valent hydrocarbon group A may have include alkyl groups, alkoxy groups, halogen atoms, and hydroxyl groups.

[0035] As the alkyl group, linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms are preferred, more preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, and cyclohexyl groups, even more preferably alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl or ethyl groups.

[0036] Examples of alkoxy groups include linear or branched alkyl groups having 1 to 16 carbon atoms, such as methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, n-octylooxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-tetradecyloxy, 2-ethylhexyloxy, 3-ethylheptyloxy, and 2-hexyldecyloxy groups. Particularly preferred are groups selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, and n-octylooxy groups.

[0037] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.

[0038] In particular, the hydrocarbon group A with an m-valence is preferably one of the linking groups consisting of the following formulas (a-1) to (a-4).

[0039] [ka]

[0040] In formulas (a-1) to (a-4), *L represents the bond position with L1 in formula (4), and the * at the end of the carbon atom represents the bond position with the oxygen atom constituting the ester group in formula (1).

[0041] The m-valent hydrocarbon group A is preferably a trivalent linking group of one of the group consisting of formulas (a-1), (a-2), and (a-3), for the sake of ease of reaction in monomer synthesis, more preferably a trivalent linking group of formula (a-1) or formula (a-2), and even more preferably a trivalent linking group of formula (a-1).

[0042] In formula (1), R2, R3, R4, R5, and R6 are the same or different and represent one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear alkyl halide having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group.

[0043] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.

[0044] As a linear alkyl group having 1 to 20 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred. Specifically, examples include methyl groups, ethyl groups, and n-propyl groups, with methyl groups or ethyl groups being preferred.

[0045] As branched alkyl groups having 3 to 20 carbon atoms, alkyl groups having 3 to 6 carbon atoms are preferred, and specifically, examples include isopropyl groups and tert-butyl groups.

[0046] As for cyclic alkyl groups having 3 to 20 carbon atoms, alkyl groups having 3 to 6 carbon atoms are preferred. Specifically, examples include cyclopropyl groups, cyclopentyl groups, and cyclohexyl groups, with cyclohexyl groups being preferred among them.

[0047] As the linear alkyl halide having 1 to 20 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms are preferred. Specifically, examples include trifluoromethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl groups, with trifluoromethyl being the most preferred.

[0048] As for alkoxy groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms are preferred, and specifically, examples include methoxy groups, ethoxy groups, n-butoxy groups, and methoxyethoxy groups.

[0049] As for the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferred. Specifically, examples include the phenyl group, α-methylphenyl group, and naphthyl group, with the phenyl group being the most preferred.

[0050] As for the aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 12 carbon atoms is preferred. Specifically, examples include the phenyloxy group and the 2-naphthyloxy group, with the phenyloxy group being the most preferred.

[0051] Examples of amino groups include primary amino groups (-NH2); secondary amino groups such as methylamino groups; and tertiary amino groups such as dimethylamino groups, diethylamino groups, dibenzylamino groups, and groups with nitrogen atoms of nitrogen-containing heterocyclic compounds (e.g., pyrrolidine, piperidine, piperazine, etc.) as the bonding site.

[0052] R2, R3, R4, R5, and R6 are preferably hydrogen atoms, alkyl groups, halogen atoms, or linear halogenated alkyl groups having 1 to 20 carbon atoms, and more preferably hydrogen atoms, in order to improve the solubility, photocurability, and liquid repellency of the fluororesin in fluororesins.

[0053] Examples of repeating units represented by formula (1) containing a photocrosslinkable group (hereinafter sometimes referred to as repeating unit B) include, for example, the repeating units B-1 to B-26 shown below, among which B-1 to B-16 are preferred, and B-1, B-2, B-13, and B-16 are particularly preferred. In the formula below, Me represents a methyl group, Et represents an ethyl group, and Pr represents an isopropyl group.

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] The fluororesin of the present invention has repeating units containing 20 mol% or more, preferably 20 mol% to 80 mol%, and particularly preferably 20 mol% to 70 mol% of fluorine atoms. As a result, the fluororesin exhibits liquid-repellent properties and also has high solubility in fluororesin solvents.

[0060] The repeating unit containing the fluorine atom is preferably a repeating unit represented by the following formula (2).

[0061] [ka]

[0062] In formula (1), R7 represents a hydrogen atom or a methyl group.

[0063] In formula (1), L2 represents a single bond or a divalent linking group.

[0064] The divalent linking group in L2 is preferably a divalent linking group that combines at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), or an imino group (-NH-). This enables the formation of a flat, crack-free film.

[0065] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0066] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-tylpropylene group.

[0067] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0068] Examples of arylene groups having 6 to 12 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0069] Of these divalent linking groups, it is more preferable that they are ester bonds (-C(=O)O-) formed by combining a carbonyl group and an ether group, or linking groups formed by combining a phenylene group and an ether group, and even more preferable that they are (-C(=O)O-).

[0070] In formula (2), Rf1 represents one of the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.

[0071] Because Rf1 is a fluoroalkyl group, the fluororesin according to one embodiment of the present invention exhibits affinity for fluororesin and liquid repellency.

[0072] If Rf1 is a linear fluoroalkyl group, specific examples of Rf1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl groups, or alkyl groups having 10 to 14 carbon atoms, all of which are substituted with a fluorine atom. If the element bonded to Rf1 in L1 is oxygen, the substitution position of the fluorine atom in Rf1 can be on any carbon atom other than the carbon atom directly bonded to the oxygen in L1.

[0073] When Rf1 is a linear fluoroalkyl group, it is preferable that Rf1 is a group represented by the following formula (3).

[0074] [ka]

[0075] In equation (3), * represents the bond position with L2 in equation (2).

[0076] In equation (3), X is either a hydrogen atom or a fluorine atom.

[0077] In equation (3), y is an integer between 1 and 4, preferably between 1 and 2.

[0078] In equation (3), z is an integer between 1 and 14, preferably between 2 and 10, and more preferably between 4 and 8.

[0079] The fact that Rf1 is a group represented by formula (3) makes it easier to synthesize monomers that serve as raw materials for the repeating unit represented by formula (1).

[0080] When Rf1 is a branched fluoroalkyl group, specific examples of Rf1 include 1,1,1,3,3,3-hexafluoroisopropyl group, 1-(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, 1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, or 1,1-bis(trifluoromethyl)ethyl group.

[0081] When Rf1 is a cyclic fluoroalkyl group, specific examples of Rf1 include the 1,2,2,3,3,4,4,5,5-nonafluorocyclopentane group and the 1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexane group.

[0082] The repeating unit represented by formula (2) above is preferably the repeating unit represented by formula (4) below.

[0083] [ka]

[0084] In formula (4), R8 represents either a hydrogen atom or a methyl group.

[0085] In equation (4), X is either a hydrogen atom or a fluorine atom.

[0086] In equation (4), y is an integer between 1 and 4, preferably between 1 and 2.

[0087] In equation (4), z is an integer between 1 and 14, preferably between 2 and 10, and more preferably between 4 and 8.

[0088] A fluororesin according to one aspect of the present invention may contain one repeating unit represented by formula (2), or it may contain two or more repeating units. For example, it may contain both repeating units having a linear fluoroalkyl group as Rf1 as described above, and repeating units having a branched fluoroalkyl group as described above, or it may contain two or more repeating units having linear fluoroalkyl groups with different numbers of carbon atoms. A fluororesin according to one aspect of the present invention preferably contains one repeating unit represented by formula (2).

[0089] In one aspect of the present invention, a repeating unit containing a fluorine atom in a fluororesin can be specifically listed as one of the group consisting of repeating units represented by the following formulas (C-1) to (C-33).

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] As the repeating unit containing a fluorine atom, one of the group consisting of repeating units represented by formulas (C-1) to (C-33) is preferred, one of the group consisting of repeating units represented by formulas (C-9) to (C-33) is more preferred, and one of the group consisting of repeating units represented by formulas (C-14) to (C-21) or one of the group consisting of repeating units represented by formulas (C-27) to (C-33) is particularly preferred.

[0094] In one aspect of the present invention, the fluororesin is preferably a copolymer containing repeating units represented by formula (1) and repeating units represented by formula (2). That is, the fluororesin in one aspect of the present invention is preferably a copolymer represented by the following formula (5).

[0095] [ka]

[0096] (In formula (5), R1 and R7 represent a hydrogen atom or a methyl group, L1 and L2 represent a single bond or a divalent linking group, A represents an m-valent linking group, and R2, R3, R4, R5, and R6, either identical or different, represent one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear alkyl halide having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 3 or more, and n represents an integer of m-1. Rf1 represents one of the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.) In equation (5), R1, L1, A, R2, R3, R4, R5, and R6 are equivalent to R1, L1, A, R2, R3, R4, R5, and R6 in equation (1).

[0097] In equation (5), R7, L2, and Rf1 are the same as R7, L2, and Rf1 in equation (2).

[0098] The copolymer represented by formula (5) may be a random copolymer or a block copolymer.

[0099] The above-mentioned fluororesin may contain other monomer repeating units, to the extent that it does not depart from the objectives of the present invention. Examples of other monomer repeating units include olefin residues such as ethylene residues, propylene residues, and 1-butene residues; vinyl aromatic hydrocarbon residues such as styrene residues and α-methylstyrene residues; vinyl carboxylate ester residues such as vinyl acetate residues, vinyl propionate residues, and vinyl pivalate residues; vinyl ether residues such as methyl vinyl ether residues, ethyl vinyl ether residues, and butyl vinyl ether residues; N-substituted maleimide residues such as N-methyl maleimide residues, N-cyclohexyl maleimide residues, and N-phenyl maleimide residues; acrylonitrile residues; and methacrylonitrile residues.

[0100] In the fluororesin of the present invention, there are no restrictions on the molecular weight, and for example, those with a molecular weight of 2,000 to 10,000,000 (g / mol) can be used. From the viewpoint of the solution viscosity and mechanical strength of the obtained resin, it is preferably 10,000 to 1,000,000 (g / mol).

[0101] A composition according to one aspect of the present invention will be described below.

[0102] A composition according to one aspect of the present invention comprises at least one of an organic solvent and a fluorine-based solvent, and a fluorine-based resin.

[0103] The aforementioned fluorine-based solvent can be any solvent that dissolves the fluorine-based resin of the present invention. By using a fluorine-based solvent as the solvent for dissolving the fluorine-based resin, damage to device components mainly composed of organic materials can be minimized during the fabrication of electronic devices by the all-printing method, and the performance of the electronic devices can be fully realized.

[0104] In the fluorine-based compound constituting the fluorine-based solvent, the fluorine atom content is preferably 50% to 70% by mass, and more preferably 55% to 70% by mass, relative to the total mass of the fluorine-based compound. If it exceeds 70% by mass, the aforementioned fluorine-based resin will not dissolve sufficiently. If it is less than 50% by mass, the surface of the organic semiconductor film may dissolve or swell when coated or printed on the organic semiconductor film.

[0105] The following fluorine-containing hydrocarbons, fluorine-containing ethers, or fluorine-containing alcohols can be preferably used as the fluorine-containing solvent in the composition of the present invention, and fluorine-containing hydrocarbons or fluorine-containing ethers can be more preferably used.

[0106] Fluorine-containing hydrocarbons have a low ozone depletion potential and are preferred as fluorine-based solvents in the compositions of the present invention. In particular, fluorine-containing hydrocarbons having 4 to 8 carbon atoms, in a linear, branched, or cyclic configuration, in which at least one hydrogen atom is substituted with a fluorine atom, are preferred because they are easy to apply.

[0107] Examples of such fluorine-containing hydrocarbons include butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, or benzene in which at least one hydrogen atom is substituted with a fluorine atom. Specifically, examples of fluorine-containing hydrocarbons include 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 2H,3H-decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, hexafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, and hexafluorobenzene.

[0108] The fluorine-containing hydrocarbon preferably has a boiling point of 200°C or lower, and more preferably 180°C or lower. When the boiling point of the fluorine-containing hydrocarbon is 200°C or lower, it is easily removed by evaporation through heating.

[0109] Examples of fluorine-containing hydrocarbons having particularly preferred boiling points include the following:

[0110] Examples include 2H,3H-decafluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and hexafluorobenzene.

[0111] Furthermore, due to its low ozone depletion potential, fluorine-containing ether can be used as a fluorine-based solvent. In particular, the fluorine-containing ether preferably has a boiling point of 200°C or lower, and more preferably 180°C or lower. When the boiling point of the fluorine-containing ether is 200°C or lower, it is easier to evaporate and remove the fluorine-containing ether from the fluorine-based resin film by heating.

[0112] Examples of preferred fluorine-containing ethers include 1,1,2,3,3,3-hexafluoro-1-(2,2,2-trifluoroethoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3,3-pentafluoropropoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3-tetrafluoropropoxy)propane, 2,2,3,3,3-pentafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane, 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane, methyl perfluorobutyl ether, or ethyl nonafluorobutyl ether.

[0113] Examples of fluorine-containing ethers having a preferred boiling point include ethyl nonafluorobutyl ether, methyl perfluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxide decafluorohexane, (1,1,1,2,3,3-hexafluoropropoxy)pentane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, and methoxyperfluoroheptene.

[0114] A fluorinated alcohol can be used as the fluorinated solvent. The fluorinated alcohol used preferably has a boiling point of 200°C or lower, and more preferably 180°C or lower. When the boiling point of the fluorinated alcohol is 200°C or lower, it is easily evaporated and removed by heating.

[0115] Examples of preferred fluorine-containing alcohols include 1H,1H-trifluoroethanol, 1H1H-pentafluoropropanol, 1H,1H-heptafluorobutanol, 2-(perfluorobutyl)ethanol, 3-(perfluorobutyl)propanol, 2-(perfluorohexyl)ethanol, 3-(perfluorohexyl)propanol, 1H,1H,3H-tetrafluoropropanol, 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol, 2H-hexafluoro-2-propanol, and 1H,1H,3H-hexafluorobutanol.

[0116] Furthermore, to further enhance the solubility of the fluororesin, two or more types of fluororesin solvents may be included.

[0117] The organic solvent used in the composition of the present invention refers to an organic solvent that does not fall under the category of a fluorine-based solvent. There are no restrictions on the organic solvent as long as it dissolves the fluorine-based resin of the present invention, including hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indan, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, and 1,2-diclo Dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanol Mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol Methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,Examples include 2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a film with desirable properties, an organic solvent with high dissolving power for fluororesins is suitable, with xylene and propylene glycol monomethyl ether acetate being preferred. A mixed solvent obtained by mixing two or more of the aforementioned solvents in appropriate proportions can also be used.

[0118] A composition of a fluororesin and an organic solvent and at least one of the fluororesin according to one aspect of the present invention preferably contains 1 wt% to 50 wt% of the fluororesin and 50 wt% to 99 wt% of the solvent.

[0119] Furthermore, a composition according to one aspect of the present invention may also contain a photosensitizer. The photosensitizer should be one that promotes the crosslinking reaction of the photocrosslinkable group.

[0120] Examples of photosensitizers include acylosins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; carbonyl compounds such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzyl; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, and tetramethylthiuram disulfide; phenones such as acetophenone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methoxybenzophenone, and 2,4,6-trimethoxybenzophenone; and p-toluenesulfonyl chloride and I-naphthalene. Examples include sulfonyl halides such as sulfonyl chloride, 1,3-benzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, and p-acetamidobenzenesulfonyl chloride; aromatic nitro compounds such as 5-nitrofluorene, 5-nitroacenaphthene, N-acetyl-4-nitro-1-naphthylamine, and vicramid; coumarins such as 7-diethylamino-3-tenoylcoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, abbisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; and dyes such as ethionine, thionine, and methylene blue. By including a photosensitizer, the fluorine-based resin according to one embodiment of the present invention can be crosslinked (insolubilized) with a lower exposure. Furthermore, two or more types of the photosensitizer can be used in combination as needed.

[0121] A composition according to one aspect of the present invention comprising a fluororesin, a photosensitizer, and at least one of an organic solvent and a fluororesin preferably contains 1 wt% to 50 wt% of the fluororesin, 50 wt% to 99 wt% of the solvent, and 0.001 wt% to 5 wt% of the photosensitizer.

[0122] A pattern, which is one aspect of the present invention, will be described below.

[0123] A pattern can be formed using the fluororesin composition of the present invention. More specifically, a photocrosslinked product is obtained on a substrate using the composition of the present invention, a pattern is formed, a dry process is performed, and then the pattern is further formed by washing with an alkaline solution and / or alcohol. This removes the ashing residue of the fluororesin, making the areas where the fluororesin has not been removed (hereinafter referred to as the outside of the pattern) liquefy-repellent and the areas where the fluororesin has been removed (hereinafter referred to as the inside of the pattern) hydrophilic.

[0124] First, a film of the composition can be formed on the surface of the substrate by a known coating method. Examples of substrates include various glass plates; polyesters such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; thermoplastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide; epoxy resins; polyester resins; and thermosetting plastic sheets such as poly(meth)acrylic resins.

[0125] For example, methods for forming the film include spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, gravure printing, flexographic printing, super flexographic printing, screen printing, inkjet printing, letterpress inversion printing, inversion offset printing, and adhesion contrast printing.

[0126] Next, the film is dried. Drying causes the solvent to evaporate, resulting in a non-sticky film. Drying conditions vary depending on the boiling point and mixing ratio of the solvent used, but preferably a wide range of 50 to 150°C and 10 to 2000 seconds is possible.

[0127] When forming a film using a printing technique, if a film with a predetermined shape, i.e., the same shape as the target pattern, is formed, exposure can cause the coating film with the predetermined shape to undergo photocrosslinking, obtaining a photocrosslinked product, which is then fixed and the pattern can be formed.

[0128] On the other hand, if a film with a predetermined shape is not formed during film formation, a pattern can be formed from the film using photolithography. When using photolithography, the dried film is first exposed to light through a mask with a predetermined shape, i.e., a shape that can form the desired pattern, and then photocrosslinked.

[0129] When a film (composition of the present invention) is cured by photocrosslinking to obtain a photocrosslinked product, radiation such as ultraviolet light and visible light is used, for example, ultraviolet light with a wavelength of 245 to 435 nm is used. The irradiation dose is appropriately changed depending on the composition of the resin, but for example, it is 10 to 5000 mJ / cm². 2 For example, to prevent a decrease in the degree of crosslinking and to improve economic efficiency by shortening the process time, the irradiation dose is preferably 100 to 4000 mJ / cm². 2 Specific examples of light irradiation devices or light sources include germicidal lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, etc.

[0130] Ultraviolet irradiation is usually carried out in the atmosphere, but can also be done in an inert gas or under a constant flow of inert gas if necessary. If necessary, the aforementioned photosensitizer can be added to promote the photocrosslinking reaction. Afterward, development is performed with a developer to remove unexposed areas. The developer can be any solvent that dissolves the uncured fluororesin, such as aromatic solvents like benzene, toluene, and xylene; ether solvents like dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone solvents like acetone and methyl ethyl ketone; ester solvents like ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate; and 2H,3H-decafluoropentane. Fluorine-based solvents such as 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, hexafluorobenzene, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H,7H-dodecafluoro-1-heptanol, and 2,2,3,3,4,4,4-heptafluoro-1-butanol can be used.

[0131] The development time is preferably 30 to 300 seconds. The development method can be any of the following: liquid buildup method, dipping method, etc. After development, the solvent on the substrate is removed by washing with a solvent and air-drying with compressed air or compressed nitrogen. Subsequently, the pattern is formed by heating with a heating device such as a hot plate or oven, preferably at 40 to 150°C for 5 to 90 minutes.

[0132] When using the above photolithography technique, after forming the pixel pattern via photolithography, the substrate surface within the pixels may be cleaned. For example, this can be done by irradiating with short-wavelength ultraviolet light such as a low-pressure mercury lamp or excimer UV, or by photo-ashing. Photo-ashing is a process in which short-wavelength ultraviolet light is irradiated in the presence of ozone gas. The short-wavelength ultraviolet light is light having a main peak at a wavelength of 100 to 300 nm.

[0133] Thus, the above-mentioned fluororesin is itself soluble in fluororesin or organic solvents, and upon light irradiation, the photocrosslinkable groups in its side chains are crosslinked and cured, becoming insoluble in the solvent used. Utilizing this property, the above-mentioned fluororesin can be used as a negative-type resist in which the unirradiated portions are removed by the fluororesin or organic solvent after crosslinking by light irradiation.

[0134] The dry process used after obtaining the photocrosslinked material and forming the pattern is preferably a dry process using at least one of a plasma device, a UV ozone device, and a reactive ion etching device, and more preferably a plasma cleaner and a UV ozone cleaner. This makes it possible to remove trace amounts of fluorine-based resin residue remaining inside the pattern and to make the inside of the pattern hydrophilic.

[0135] The ashing residue present on substrates that have undergone the dry process is a modified product of the fluororesin used in the dry process. It adheres to the outside and inside of the pattern, increasing resistance and reducing the hydrophilicity inside the pattern and the liquid-repellent properties outside the pattern. Since this modified product consists of oxidized fluororesin, it forms an insulating layer.

[0136] To remove ashing residue, a dry process is performed, followed by further washing with an alkaline solution and / or alcohol (ashing residue removal process).

[0137] The above-mentioned alkaline solution is preferably an aqueous solution of an alkali containing at least one of the following: inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, or cyclic amines.

[0138] Examples of inorganic alkalis include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.

[0139] Examples of primary amines include ethylamine and n-propylamine.

[0140] Examples of secondary amines include diethylamine and di-n-butylamine.

[0141] Examples of tertiary amines include triethylamine and methyldiethylamine.

[0142] Examples of alcohol amines include dimethylethanolamine and triethanolamine.

[0143] Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.

[0144] Examples of cyclic amines include pyrrole and piperidine.

[0145] Among these, inorganic alkalis, tertiary amines, alcohol amines, and quaternary ammonium salts are preferred as alkaline solutions, with quaternary ammonium salts being particularly preferred.

[0146] The hydrogen ion concentration index of the above alkaline solution is preferably pH 8 or higher, more preferably pH 10 or higher, and even more preferably pH 12 or higher.

[0147] The alcohols mentioned above are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, etc., are used, with methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol being preferred.

[0148] Cleaning (treatment) with alkaline solution and / or alcohol can be performed, for example, by bringing a substrate that has undergone a dry process into contact with an alkaline solution and / or alcohol. The contact conditions with the alkaline solution and / or alcohol can be set appropriately according to the type and temperature of the alkaline solution and / or alcohol, so as to remove the ashing residue after the dry process.

[0149] Various contact methods are used, such as a batch method in which a large quantity of materials to be treated in a cassette is immersed in a tank containing an alkaline solution and / or alcohol; a sheet-fed method in which an alkaline solution and / or alcohol is poured over a rotating material to clean it; and a spray method in which an alkaline solution and / or alcohol is continuously sprayed onto the material to be treated for cleaning.

[0150] The temperature in the ashing residue removal process should be, for example, around 10 to 60°C, preferably around 15 to 40°C.

[0151] The contact time is not limited and can be selected as appropriate, but examples include approximately 0.5 to 60 minutes, preferably 0.5 to 10 minutes.

[0152] In the case of batch processing, the workpiece may be immersed in an alkaline solution and / or alcohol under stirring, if necessary. The stirring speed is not limited and can be selected as appropriate. If unwanted materials are difficult to remove, for example, the workpiece may be immersed in an alkaline solution and / or alcohol and then ultrasonically cleaned.

[0153] After the ashing residue removal process, the surface can be further washed with pure water. This washing process can rinse away alkaline solutions and / or alcohol.

[0154] In the patterns obtained by the pattern forming method of the present invention, the portion where the fluororesin remains crosslinked (outside the pattern) avoids the wetting and spreading of the ink for forming the functional layer and exhibits excellent liquid repellency. Therefore, the contact angle (water contact angle outside the pattern) is preferably 70° or more, and particularly preferably 80° or more.

[0155] Furthermore, since the areas where the fluororesin has been removed (inside the pattern) exhibit excellent hydrophilicity, the contact angle (water contact angle inside the pattern) is preferably 30° or less, more preferably 20° or less, and particularly preferably 10° or less.

[0156] The present invention provides a pattern formation method that includes an ashing residue removal step, which effectively removes ashing residue present on a substrate after a dry process. This method makes the pattern more hydrophilic when manufacturing organic transistor elements, color filters, and organic EL elements, allowing the ink to wet and spread more easily. Furthermore, it can improve the electrical properties of electronic vices including the aforementioned organic transistor elements, color filters, and organic EL elements.

[0157] An electronic device according to one aspect of the present invention will be described in detail below.

[0158] The ashing residue removal process of the present invention can be used in electronic devices.

[0159] Organic transistors can be cited as an example of electronic devices.

[0160] A typical organic transistor has a gate insulating layer on a substrate, and an organic semiconductor layer is deposited on this gate insulating layer, with a source electrode, drain electrode, and gate electrode attached. An example of the device structure of an organic transistor is shown in cross-sectional view in Figure 1. 1001 is a bottom gate-top contact type, 1002 is a bottom gate-bottom contact type, 1003 is a top gate-top contact type, and 1004 is a top gate-bottom contact type device structure. 1 is the organic semiconductor layer, 2 is the substrate, 3 is the gate electrode, 4 is the gate insulating layer, 5 is the source electrode, and 6 is the drain electrode.

[0161] Figure 2 shows one form of the organic transistor described above. The organic transistor 1005 shown in Figure 2 corresponds to the bottom-gate-bottom-contact type in Figure 1. 7 indicates the pattern, and 8 indicates the protective film layer.

[0162] In this organic transistor, the substrate that can be used is not particularly limited as long as sufficient flatness can be ensured to fabricate the element. Examples include inorganic material substrates such as glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; and surface-coated nonwoven fabrics. Composite materials made of these materials or multilayer materials made of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

[0163] Examples of plastics that can be used as substrates include polyethylene terephthalate, polyethylene naphthalate, triacetylcellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, and styrene block copolymer. Furthermore, two or more of the above plastics can be used to laminate and form a substrate.

[0164] There are no restrictions on the organic semiconductors that can be used in the organic semiconductor layer; both N-type and P-type organic semiconductors can be used, and they can also be used as bipolar transistors combining N-type and P-type semiconductors. Furthermore, both low-molecular-weight and high-molecular-weight organic semiconductors can be used, and these can also be used in mixtures. Specific examples of organic semiconductor compounds include those represented by the following formulas (D-1) to (D-11).

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] In the present invention, examples of methods for forming an organic semiconductor layer include vacuum deposition of an organic semiconductor, or coating or printing by dissolving an organic semiconductor in an organic solvent. However, there are no limitations as long as a method capable of forming a thin film of the organic semiconductor layer is used. When coating or printing using a solution obtained by dissolving an organic semiconductor layer in an organic solvent, the solution concentration varies depending on the structure of the organic semiconductor and the solvent used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the thickness of the layer, it is preferably 0.5 to 5 wt%. As long as the organic solvent used in this process dissolves the organic semiconductor at a certain concentration that allows for film formation, there are no restrictions. Examples include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indan, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, and 3 - Methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,Examples include 8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a crystalline film with desirable properties, a solvent with high dissolving power for organic semiconductors and a boiling point of 100°C or higher is suitable. Xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. A mixed solvent obtained by mixing two or more of the aforementioned solvents in appropriate proportions can also be used.

[0170] The organic semiconductor layer may contain, as needed, various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles in solid form or dispersions in water or an organic solvent. A polymer solution can be applied to the insulating layer to form a protective film. Furthermore, various moisture-proof coatings, light-resistant coatings, etc., can be applied to this protective film as needed.

[0171] Examples of conductive materials that can be used as gate electrodes, source electrodes, or drain electrodes in the present invention include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, platinum, titanium, tantalum, graphene, and carbon nanotubes, or organic electrodes such as doped conductive polymers (e.g., PEDOT-PSS). Multiple layers of these conductive materials can also be used. Furthermore, to increase the carrier implantation efficiency, these electrodes can be surface-treated using a surface treatment agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

[0172] Furthermore, there are no particular limitations on the method of forming electrodes on the substrate, insulating layer, or organic semiconductor layer, and examples include vapor deposition, high-frequency sputtering, electron beam sputtering, etc. Methods such as solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, super flexographic printing, screen printing, inkjet printing, and letterpress inversion printing can also be employed using an ink obtained by dissolving nanoparticles of the conductive material in water or an organic solvent.

[0173] An organic transistor according to one aspect of the present invention has a mobility of 0.20 cm, from the viewpoint of the practicality of the organic transistor element. 2 It is preferable that it is greater than or equal to / Vs.

[0174] An organic transistor according to one aspect of the present invention has an on-current / off-current ratio of 10, from the viewpoint of the practicality of the organic transistor element. 5 It is preferable that the above conditions are met.

[0175] In one aspect of the present invention, it is preferable that the organic transistor has no source-drain current hysteresis, from the viewpoint of the practicality of the organic transistor element. [Examples]

[0176] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0177] In the examples, the following conditions and equipment were used.

[0178] <Composition of fluororesin> Using a nuclear magnetic resonance measuring device (manufactured by JEOL Ltd., trade name JNM-ECZ400S), proton nuclear magnetic resonance spectroscopy ( 1 1H-NMR) spectrum analysis was used to determine it.

[0179] <Spin coating> MS-A100 manufactured by Mikasa Co., Ltd. was used.

[0180] <UV irradiation> Using a UV mask aligner, UPE-1605MA manufactured by USHIO Lighting Co., Ltd., under the condition of a UV intensity of 14.2 mW / cm 2 The UV irradiation time was adjusted by changing the conveyance speed.

[0181] <UV ozone cleaner> Using a UV ozone cleaner UV-1 manufactured by Samco Inc., a dry process was performed under the condition of an oxygen flow rate of 0.5 L / min.

[0182] In the examples, the following results were obtained.

[0183] Synthesis Example 1 (Synthesis of Photocrosslinkable Monomer 1) Under a nitrogen atmosphere, 6 g of glycerin monomethacrylate (Bremmer GLM, NOF Corporation), 8.6 g of triethylamine, and 18 g of tetrahydrofuran were placed in a 200 mL flask and thoroughly mixed. Also under a nitrogen atmosphere, 14.1 g of cinnamic chloride and 42 g of tetrahydrofuran were dissolved in a glass bottle. Then, nitrogen was passed through the flask containing the glycerin monomethacrylate, triethylamine, and tetrahydrofuran, and the cinnamic chloride solution was added dropwise using a dropping funnel, stirring for 22 hours. Afterward, the mixture was filtered to remove the by-product salt, and tetrahydrofuran was removed using an aspirator. The product was then dissolved in 50 g of toluene, washed three times with an aqueous sodium bicarbonate solution, and vacuum-dried. The resulting substance after drying... 1 ¹H-NMR and gas chromatography analysis confirmed that the substance is represented by the following formula (7) (photocrosslinkable monomer 1). (GC purity 87%) (Photocrosslinkable monomer 1)

[0184] [ka]

[0185] Example 1 (Polymerization of fluororesin 1) In a 75 mL glass ampoule, 6.78 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 9.10 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylic acid, 0.27 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, and 37 g of 2-butanone were placed. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and maintaining it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 500 mL of methanol, and then washed twice with 300 mL of methanol. Further vacuum drying at 30°C for 8 hours yielded 13.8 g of fluororesin 1 (yield: approximately 87%). 1By \(^1\)H-NMR measurement, the composition was confirmed to be a copolymer represented by the formula (7), with the composition of photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit) [C-29] = 38 / 62 (mol%). 1 The \(^1\)H-NMR measurement results are shown in Figure 3.

[0186] (Fluorine-based resin 1)

[0187] [Chemical formula]

[0188] Example 2 (Polymerization of fluorine-based resin 2) Into a 75 mL glass ampoule, 8.2 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 3.1 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.18 g of Perhexyne ND (manufactured by NOF Corporation) as a polymerization initiator, and 26 g of 2-butanone were placed. After repeating nitrogen substitution and pressure release, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 °C and held for 24 hours to conduct radical polymerization. After the polymerization reaction was completed, the polymer solution was taken out from the ampoule, dropped into 500 mL of methanol for precipitation, and then washed twice with 300 mL of methanol. Further, by vacuum drying at 30 °C for 8 hours, 8.8 g of fluorine-based resin 9 was obtained (yield: about 88%). 1 By \(^1\)H-NMR measurement, the composition was confirmed to be a copolymer represented by the formula (8), with the composition of photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 26 / 74 (mol%).

[0189] (Fluorine-based resin 2)

[0190] [Chemical formula] ​

[0191] Comparative Example 1 (Polymerization of Fluorine-based Resin 3) In a 75 mL glass ampoule, 10.9 g of the photocrosslinkable monomer obtained in Synthesis Example 1, 0.72 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylic acid, 0.18 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, and 27 g of 2-butanone were placed. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and maintaining it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, precipitated by dropping it into 500 mL of methanol, and then washed twice with 300 mL of methanol. Further vacuum drying at 30°C for 8 hours yielded 8.5 g of fluoropolymer resin 9 (yield: approximately 85%). 1 ¹H-NMR measurement confirmed that its composition is photocrosslinkable monomer 1 (photocrosslinking group unit 1)[B-1] / methacrylic acid 1H,1H,2H,2H-tridecafluoro-n-octyl (fluorine system unit 1)[C-29] = 10 / 90 (mol%), and that it is a copolymer represented by formula (9).

[0192] (Fluorine-based resin 3)

[0193] [ka]

[0194] <Evaluation of removal of ashing residue after dry process> (Evaluation of ashing residue removal in areas where fluoropolymer resin has been removed) A solution was prepared by adding the synthesized fluororesins 1-3 and 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a sensitizer, resulting in a solution with a concentration of 20 wt% fluororesin and 0.4 wt% sensitizer. (Solvent: propylene glycol monomethyl ether acetate) The solution was then washed and dried. 30 x 30 mm 2A solution of fluoropolymer resin 1-2 was spin-coated onto Corning EagleXG glass at 500 rpm for 5 seconds and 1500 rpm for 20 seconds, and then dried at 150°C for 10 minutes. A 15 x 20 mm mask was used for pattern formation. 2 A mask with a chrome pattern was used for the shape. 30 x 30 mm 2 A mask is placed on a film obtained by spin-coating the above solution onto a glass substrate, and UV light is applied at 300 mJ / cm². 2 Irradiation was performed. After irradiation, the uncrosslinked portions were washed off with acetone for 1 minute, resulting in a 15 x 20 mm layer on the film. 2 A pattern of shape and size was formed.

[0195] Subsequently, the material was treated with a UV ozone device for 10 minutes as a dry process, followed by treatment at 150°C for 1 minute. After that, to remove the ashing residue, it was washed with alcohol or alkaline solution (washing solutions 1 and 2) and dried at 150°C for 1 minute.

[0196] Subsequently, a contact angle meter (Kyowa Interface Chemical Co., Ltd., product name DM-300) was used to measure the contact angle with water in the area where the fluoropolymer resin had been removed (inside the pattern) using the θ / 2 method. The results are shown in Table 1.

[0197] The evaluation results showed that removing the ashing residue reduced the water contact angle inside the pattern to 10° or less, confirming that it became hydrophilic.

[0198] Washing solution 1: 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo, NMD-3) Cleaning solution 2: Isopropyl alcohol (Evaluation of ashing residue removal in areas where fluoropolymer resin has not been removed) A solution was prepared by adding the synthesized fluororesins 1-3 and 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a sensitizer, resulting in a solution with a concentration of 20 wt% fluororesin and 0.4 wt% sensitizer. (Solvent: propylene glycol monomethyl ether acetate) The solution was then washed and dried. 30 x 30 mm 2A solution of fluoropolymer resin 1-2 was spin-coated onto Corning EagleXG glass at 500 rpm for 5 seconds and 1500 rpm for 20 seconds, dried at 150°C for 10 minutes, and exposed to UV light at 300 mJ / cm². 2 The material was cured by irradiation. Then, as a dry process, it was treated with a UV ozone device for 10 minutes. Afterward, to remove the ashing residue, it was washed with alcohol or alkaline solution (washing solutions 1 and 2) and dried at 150°C for 1 minute.

[0199] Subsequently, a contact angle meter (Kyowa Interface Chemical Co., Ltd., product name DM-300) was used to measure the contact angle with water in the area where the fluoropolymer resin had not been removed (outside the pattern) using the θ / 2 method. The results are shown in Table 1.

[0200] The evaluation results showed that in Examples 1 and 2, which used fluoropolymer resins 1 and 2, the water contact angle outside the pattern was 80° or more after removing the ashing residue, indicating liquefaction, while the water contact angle inside the pattern was 10° or less, confirming that it had liquefied.

[0201] On the other hand, Comparative Example 1, which used fluorine-based resin 3 with a fluorine atom content of less than 20 mol%, had a contact angle of 80° or less outside the pattern, indicating that it did not sufficiently repel liquid.

[0202] [Table 1] [Explanation of symbols]

[0203] 1 Organic semiconductor layer 2 circuit boards 3. Foodstuffs 4 Gate Insulation Layer 5 Source electrodes 6 Drain electrode 7 patterns 8 Protective film layer

Claims

1. A fluororesin having a substrate containing repeating units represented by the following formula (1) which include photocrosslinkable groups, and 20 mol% or more of repeating units represented by the following formula (2) which include fluorine atoms, A method for forming a pattern, characterized by obtaining a photocrosslinked product using a composition containing at least one of an organic solvent and a fluorine-based solvent, forming a pattern, performing a dry process, and then further washing with an alkaline solution and / or alcohol. 【Chemistry 1】 (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ represents an ester bond (-C(=O)O-) combining a carbonyl group and an ether group, or a linking group combining a phenylene group and an ether group, A represents one type of linking group from the group consisting of the following formulas (a-1) to (a-4), R ２ , R ３ , R ４ , R ５ and R ６ (where n represents a hydrogen atom, and n represents 2.) 【Chemistry 2】 【Transformation 3】 (In formula (2), R ７ represents a hydrogen atom or a methyl group. L ２ represents an ester bond (—C(═O)O—) combining a carbonyl group and an ether group or a linking group combining a phenylene group and an ether group, and Rf １ represents a group represented by the following formula (3).) 【Chemistry 4】 (In equation (3), * represents L in equation (2) ２ This represents the bonding position, where X is a hydrogen atom or a fluorine atom, y is an integer from 1 to 4, and z is an integer from 1 to 14.

2. The method for forming a pattern according to claim 1, wherein the alkaline solution is an aqueous solution of an alkali containing at least one of inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, and cyclic amines.

3. The method for forming a pattern according to claim 1, wherein the alcohol is a saturated aliphatic alcohol having 1 to 4 carbon atoms.

4. A method for forming a pattern according to any one of claims 1 to 3, wherein the dry process is a dry process using at least one of a plasma device, a UV ozone device, and a reactive ion etching device.

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