Fluorine-based resin, composition, photocrosslinked product, and electronic device including same

Abstract

Provided is a fluorine resin that has a liquid repellence property, is highly dissolvable in fluorine-based solvents, and is made insoluble in solvents by photocrosslinking using a low quantity of light exposure. A fluorine resin according to the present invention has a repeating unit that is represented by formula (1) and includes a photocrosslinkable group, and a repeating unit that includes a fluorine atom.　(In the formula, R1 represents hydrogen or methyl, L1 represents a single bond or a linking group, A represents a linking group, and R2-R6 each represent one option among the group consisting of hydrogen, a halogen, an alkyl, a halogenated alkyl, an alkoxy group, an aryl, an aryloxy group, a cyano group, and an amino group.

Description

[Technical Field]

[0001] The present invention relates to a fluororesin, and more particularly to a fluororesin that can be suitably used in electronic devices. [Background technology]

[0002] In recent years, technological developments have been actively pursued for the low-cost, highly productive fabrication of organic electronic devices using all-printing methods. One example of such electronic devices is the development of organic transistors. These organic transistors are manufactured through a number of processes, including a process in which a protective resin film protects the organic transistor and forms a pattern of an EL light-emitting element. This pattern is formed to cover, for example, the source electrode, the drain electrode, and the organic semiconductor layer or polymer layer, but is not present on the electrodes that form the EL light-emitting element.

[0003] Typically, EL light-emitting areas are formed using photolithography, a technology in which a substrate surface coated with a photosensitive material (resist) is exposed to a pattern through a photomask or reticle, forming a pattern consisting of exposed and unexposed areas. In photolithography, the EL light-emitting areas are opened by dry etching or wet etching.

[0004] Photoreactive polymeric materials are used as pattern-forming materials. In coating methods such as full-scale printing, the material is dissolved in a solvent and applied as an ink. After the solvent is dried and removed, the material is insolubilized in the solvent by photocrosslinking to form a pattern. Therefore, polymeric materials used in coating methods such as full-scale printing are required to have both excellent solubility in the solvent and the ability to undergo photocrosslinking at room temperature and with short exposure to light after solvent removal.

[0005] Here, we will explain the method for manufacturing organic electroluminescent devices used in organic electroluminescent displays and organic electroluminescent lighting. First, the polymer material is applied to a substrate, and the area where you want to form a pattern is photocrosslinked, and the area that has not been photocrosslinked is removed. This leaves the remaining area as the pattern. Various functional layers are then laminated in the area where the polymer material has been removed (inside the pattern). A promising technology for forming the functional layers is to use ink-like raw materials, but from the perspective of preventing ink adhesion inside the pattern and ink leakage beyond the area where the polymer material has not been removed (outside the pattern), it is expected that the material that makes up the pattern will have liquid-repellent properties.

[0006] Furthermore, in organic semiconductor elements, when forming an interlayer insulating film or a gate insulating film on a source electrode, a drain electrode, and an organic semiconductor layer, it is expected that patterns can be formed by photolithography without damage, and contact holes and the like can be formed in the insulating film.

[0007] Patent Document 1 lists such a material as a negative photosensitive resin composition that is highly photoreactive, allows patterning, and can form a coating with excellent dielectric properties, as well as a photocured pattern produced from the composition. However, this resin requires the use of water or an organic solvent during development. Furthermore, the composition requires the use of an organic solvent such as PGMEA (propylene glycol monomethyl ether acetate). Both organic solvents and water can cause a decrease in the performance of electronic devices. Therefore, there was a need to develop a material that can be used with a fluorine-based solvent to prevent a decrease in the performance of electronic devices.

[0008] As such a technique, there is a method of forming a pattern using a fluorine-based resin that is soluble in a fluorine-based solvent, as disclosed in Patent Document 2 and Non-Patent Document 1. However, there is a problem that such a fluorine-based resin does not undergo photocrosslinking.

[0009] Examples of fluorine-based resins that dissolve in fluorine-based solvents and undergo photocrosslinking include fluorine-based resins that use anthracene crosslinking groups, such as those disclosed in Non-Patent Document 2. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2017-167513 [Patent Document 2] Japanese Patent No. 6281427 [Non-patent literature]

[0011] [Non-Patent Document 1] Appl. Phys. Express 7, 101602 (2014) [Non-patent document 2] J Polym Sci A Polym Chem 53, 1252(2015) Summary of the Invention [Problem to be solved by the invention]

[0012] However, the fluororesin described in Non-Patent Document 2 has low photocrosslinkability and requires a high exposure dose, so there is a demand for a fluororesin with high photoreactivity.

[0013] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a fluorine-based resin that has liquid-repellent properties, is highly soluble in fluorine-based solvents, and can be made insoluble in solvents by photocrosslinking with a low exposure dose. [Means for solving the problem]

[0014] As a result of extensive research into solving the above problems, the present inventors have found that a fluororesin having a specific structure can solve the above problems, and have thus completed the present invention.

[0015] That is, the present invention is a fluororesin having a repeating unit represented by the following formula (1) containing a photocrosslinkable group and a repeating unit containing a fluorine atom.

[0016] That is, the present invention has the following gist.

[0017] [1] A fluororesin having a repeating unit represented by the following formula (1) containing a photocrosslinkable group and a repeating unit containing a fluorine atom: [ka] (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 represent one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group of 1 to 20 carbon atoms, a branched alkyl group of 3 to 20 carbon atoms, a cyclic alkyl group of 3 to 20 carbon atoms, a linear halogenated alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 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 equal to or greater than m-1.) [2] The fluorine-containing resin according to [1], further comprising a repeating unit represented by the following formula (2): [ka] (In formula (2), R7 represents a hydrogen atom or a methyl group, and R8 represents an alkyl group having 1 to 30 carbon atoms.) [3] The fluorine-containing resin according to [1] or [2], wherein the repeating unit containing a fluorine atom is a repeating unit represented by the following formula (3): [ka] (In formula (3), R9 represents a hydrogen atom or a methyl group. L2 represents a single bond or a divalent linking group. Rf1 represents one type of 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.) [4] The fluorine-containing resin according to any one of [1] to [3], wherein in the formula (1), A is one kind of linking group selected from the group consisting of the following formulae (a-1) to (a-4): [ka] (In formulas (a-1) to (a-4), *L represents the bonding position with L1 in formula (1), and * before the carbon atom represents the bonding position with the oxygen atom constituting the ester group in formula (1).) [5] The fluorine-containing resin according to [4], wherein in the formula (1), A is a linking group of the formula (a-1).

[0018] [6] The fluorine-based resin according to any one of [1] to [5], which is soluble in a fluorine-based solvent.

[0019] [7] A composition comprising the fluorine-containing resin according to any one of [1] to [6] and at least one solvent selected from an organic solvent and a fluorine-containing solvent.

[0020] [8] A photocrosslinked product of the fluororesin according to any one of [1] to [6] or the composition according to [7].

[0021] [9] A pattern composed of the photo-crosslinked product described in [8].

[0022]

[10] An electronic device comprising the photocrosslinked product according to [8]. [Effects of the Invention]

[0023] According to the present invention, a fluororesin having liquid repellency, high solubility in fluorine-containing solvents, and insolubilizable in the solvents by photocrosslinking at a low exposure dose can be obtained. The fluororesin can be used for pattern formation, and by forming a pattern using the fluororesin, deterioration in the performance of the resulting electronic device can be prevented. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 is a diagram showing a cross-sectional shape of an organic transistor. [Figure 2] FIG. 1 is a diagram showing a cross-sectional shape of an organic transistor, which is one embodiment of an electronic device of the present invention. [Figure 3] FIG. 1 is a diagram showing a 1H-NMR chart of fluororesin 1 produced in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0025] The fluorine-based resin according to one embodiment of the present invention will be described in detail below.

[0026] The fluororesin of the present invention is a fluororesin having a repeating unit represented by the following formula (1) and a repeating unit containing a fluorine atom. [ka] The fluororesin of the present invention has a photocrosslinkable group, which allows the fluororesin to exhibit high photoreactivity and selectively insolubilize only the light-irradiated portions of the film obtained by coating the resin.

[0027] In formula (1), R1 represents a hydrogen atom or a methyl group.

[0028] In formula (1), L1 represents a single bond or a divalent linking group.

[0029] The divalent linking group in L1 is preferably a divalent linking group combining 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)-), and an imino group (-NH-). This allows for the formation of a flat, crack-free film.

[0030] Specific examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.

[0031] Specific examples of the branched alkylene group having 3 to 10 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-ethylpropylene group.

[0032] Specific examples of the cyclic alkylene group having 3 to 10 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-tetrahydrodicyclopentadiene-diyl group, and among these, a cyclohexylene group is preferred.

[0033] Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and among these, a phenylene group is preferred.

[0034] Of these divalent linking groups, an ester bond (—C(═O)O—) formed by combining a carbonyl group and an ether group, or a linking group formed by combining a phenylene group and an ether group is more preferred, and (—C(═O)O—) is even more preferred.

[0035] In formula (1), A represents a linking group having a valence of m.

[0036] m represents an integer of 3 or more, preferably an integer of 3 to 5, more preferably an integer of 3 to 4, and even more preferably 3.

[0037] A may be an m-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, since this improves the solubility of the resulting resin in organic solvents and fluorine-containing solvents.

[0038] Examples of the substituent that the m-valent hydrocarbon group A may have include an alkyl group, an alkoxy group, a halogen atom, and a hydroxyl group.

[0039] The alkyl group is preferably, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms; more preferably, an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, or a cyclohexyl group; still more preferably, an alkyl group having 1 to 4 carbon atoms; and particularly preferably, a methyl group or an ethyl group.

[0040] Examples of the alkoxy group include alkoxy groups having a straight-chain or branched alkyl group having 1 to 16 carbon atoms, such as methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-tetradecyloxy, 2-ethylhexyloxy, 3-ethylheptyloxy, and 2-hexyldecyloxy groups, and groups selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, and n-octyloxy groups are particularly preferred.

[0041] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.

[0042] Among these, the m-valent hydrocarbon group A is preferably one type of linking group selected from the group consisting of the following formulae (a-1) to (a-4). [ka] In formulas (a-1) to (a-4), *L represents the bonding position with L1 in formula (1), and * before the carbon atom represents the bonding position with the oxygen atom constituting the ester group in formula (1).

[0043] For ease of reaction in monomer synthesis, the m-valent hydrocarbon group A is preferably a trivalent linking group of one type selected from the group consisting of formula (a-1), formula (a-2), and formula (a-3), 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).

[0044] In formula (1), R2, R3, R4, R5, and R6 may be 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 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.

[0045] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.

[0046] As the linear alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferred, and specific examples include a methyl group, an ethyl group, and an n-propyl group, with a methyl group or an ethyl group being particularly preferred.

[0047] As the branched alkyl group having 3 to 20 carbon atoms, an alkyl group having 3 to 6 carbon atoms is preferred, and specific examples include an isopropyl group and a tert-butyl group.

[0048] As the cyclic alkyl group having 3 to 20 carbon atoms, an alkyl group having 3 to 6 carbon atoms is preferred, and specific examples include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, with a cyclohexyl group being particularly preferred.

[0049] As the linear halogenated alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms is preferred. Specific examples include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group, and among these, a trifluoromethyl group is preferred.

[0050] As the alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms is preferable, and specific examples include a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group.

[0051] As the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferred, and specific examples include a phenyl group, an α-methylphenyl group, and a naphthyl group, with a phenyl group being particularly preferred.

[0052] As the aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 12 carbon atoms is preferred, and specific examples include a phenyloxy group and a 2-naphthyloxy group, with the phenyloxy group being particularly preferred.

[0053] Examples of amino groups include primary amino groups (-NH2); secondary amino groups such as a methylamino group; and tertiary amino groups such as a dimethylamino group, a diethylamino group, a dibenzylamino group, and groups in which the nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, piperazine, etc.) serves as a bond.

[0054] R2, R3, R4, R5 and R6 are preferably a hydrogen atom, an alkyl group, a halogen atom or a linear halogenated alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, in order to further increase the solubility in fluorine-based solvents, photocurability and liquid repellency of the fluorine-based resin.

[0055] Specific examples of the repeating unit containing a photocrosslinkable group and represented by formula (1) (hereinafter sometimes referred to as repeating unit B) include repeating units B-1 to B-26 shown below, of which B-1 to B-16 are preferred, with B-1, B-2, B-13 and B-16 being particularly preferred. In the following formulae, Me represents a methyl group, Et represents an ethyl group and Pr represents an isopropyl group. [ka] [ka] [ka] [ka] [ka] The fluororesin of the present invention has a repeating unit containing a fluorine atom, which allows the fluororesin to exhibit liquid repellency and high solubility in fluorine-containing solvents.

[0056] The repeating unit containing a fluorine atom is preferably a repeating unit represented by the following formula (3). [ka]

[0057] In formula (3), R9 represents a hydrogen atom or a methyl group.

[0058] In formula (3), L2 represents a single bond or a divalent linking group.

[0059] The divalent linking group in L2 is preferably a divalent linking group formed by combining 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 20 carbon atoms, a cyclic alkylene group having 3 to 20 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 allows for the formation of a flat, crack-free film.

[0060] Specific examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.

[0061] Specific examples of the branched alkylene group having 3 to 10 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-ethylpropylene group.

[0062] Specific examples of the cyclic alkylene group having 3 to 10 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-tetrahydrodicyclopentadiene-diyl group, and among these, a cyclohexylene group is preferred.

[0063] Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and among these, a phenylene group is preferred.

[0064] Of these divalent linking groups, an ester bond (—C(═O)O—) formed by combining a carbonyl group and an ether group, or a linking group formed by combining a phenylene group and an ether group is more preferred, and (—C(═O)O—) is even more preferred.

[0065] In formula (3), 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.

[0066] Since Rf1 is a fluoroalkyl group, the fluorine-based resin according to one aspect of the present invention exhibits affinity with fluorine-based solvents and liquid repellency.

[0067] When Rf1 is a linear fluoroalkyl group, specific examples of Rf1 include a fluorine atom-substituted methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or an alkyl group having 10 to 14 carbon atoms. When the bonding element of L2 to Rf1 is oxygen, the substitution position of the fluorine atom in Rf1 may be on a carbon atom other than the carbon atom directly bonded to the oxygen of L2.

[0068] When Rf1 is a linear fluoroalkyl group, Rf1 is preferably a group represented by the following formula (4). [ka] In formula (4), * represents the bonding position with L2 in formula (4).

[0069] In formula (4), X is a hydrogen atom or a fluorine atom.

[0070] In the formula (4), y is an integer of 1 to 4, preferably 1 to 2.

[0071] In formula (4), z is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

[0072] When Rf1 is a group represented by formula (4), it becomes easier to synthesize a monomer that serves as a raw material for the repeating unit represented by formula (3).

[0073] When Rf1 is a branched fluoroalkyl group, specific examples of Rf1 include a 1,1,1,3,3,3-hexafluoroisopropyl group, a 1-(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, a 1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, and a 1,1-bis(trifluoromethyl)ethyl group.

[0074] When Rf1 is a cyclic fluoroalkyl group, specific examples of Rf1 include a 1,2,2,3,3,4,4,5,5-nonafluorocyclopentane group and a 1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexane group.

[0075] The repeating unit represented by the formula (3) is preferably a repeating unit represented by the following formula (5). [ka] In formula (5), R 10 represents either a hydrogen atom or a methyl group.

[0076] In formula (5), X is a hydrogen atom or a fluorine atom.

[0077] In formula (5), y is an integer of 1 to 4, preferably 1 or 2.

[0078] In formula (5), z is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

[0079] The fluororesin according to one embodiment of the present invention may contain one or more repeating units represented by formula (3). For example, it may contain both a repeating unit having the linear fluoroalkyl group described above as Rf1 and a repeating unit having the branched fluoroalkyl group described above as Rf1, or it may contain two or more repeating units having linear fluoroalkyl groups with different carbon numbers. The fluororesin according to one embodiment of the present invention preferably contains one repeating unit represented by formula (3).

[0080] Specific examples of the repeating unit containing a fluorine atom in the fluorine-based resin according to one embodiment of the present invention include one type selected from the group consisting of repeating units represented by the following formulae (C-1) to (C-33). [ka] [ka] [ka] As the repeating unit containing a fluorine atom, one of the group consisting of repeating units represented by the formulae (C-1) to (C-33) is preferred, one of the group consisting of repeating units represented by the formulae (C-9) to (C-33) is more preferred, and one of the group consisting of repeating units represented by the formulae (C-14) to (C-21) or the group consisting of repeating units represented by the formulae (C-27) to (C-33) is particularly preferred.

[0081] The fluororesin according to one aspect of the present invention is preferably a copolymer containing a repeating unit represented by the formula (1) and a repeating unit represented by the formula (3). That is, the fluororesin according to one aspect of the present invention is preferably a copolymer represented by the following formula (6): [ka] (In formula (6), R1 and R9 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; 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 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; n represents an integer equal to or greater than m-1; and 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, and a cyclic fluoroalkyl group having 3 to 15 carbon atoms.) In formula (6), R1, L1, A, R2, R3, R4, R5 and R6 have the same meanings as R1, L1, A, R2, R3, R4, R5 and R6 in formula (1).

[0082] In formula (6), R9, L2 and Rf1 have the same meanings as R9, L2 and Rf1 in formula (3).

[0083] The copolymer represented by formula (6) may be a random copolymer or a block copolymer.

[0084] The fluororesin according to one aspect of the present invention preferably contains 10 mol % to 90 mol % of repeating units represented by formula (1), more preferably 20 mol % to 80 mol %, and even more preferably 20 mol % to 70 mol % of repeating units represented by formula (1), from the viewpoint of increasing solubility in fluorine-based solvents and enabling more efficient photocuring.

[0085] The content of repeating units containing fluorine atoms is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 80 mol %, and even more preferably 30 mol % to 80 mol %.

[0086] The fluororesin according to one aspect of the present invention preferably further has a repeating unit represented by formula (2). [ka] In formula (2), R7 represents a hydrogen atom or a methyl group.

[0087] In the formula (2), R8 represents an alkyl group having 1 to 30 carbon atoms.

[0088] In formula (2), R8 represents an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, and docosyl groups; isopropyl, isobutyl, isovaleryl, isohexyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, and 2-hexylundecyl. branched alkyl groups such as octyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-decylhexadecyl, 3-hexyldecyl, 3-octyldecyl, 3-octyldodecyl, 3-decyltetradecyl, 3-decylhexadecyl, 4-hexyldecyl, 4-octyldecyl, 4-octyldodecyl, 4-decyltetradecyl, 4-decylhexadecyl, 4-cyclohexylbutyl, and 8-cyclohexyloctyl; and cyclic alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, 3-decylcyclopentyl, and 4-decylcyclohexyl. Among these, one of the group consisting of a linear alkyl group having 1 to 15 carbon atoms and a branched alkyl group having 3 to 15 carbon atoms is preferred, a linear alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is more preferred.

[0089] Specific examples of the repeating unit represented by formula (2) include one type of repeating unit represented by methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and nonyl (meth)acrylate.

[0090] In the fluorine-based resin according to one aspect of the present invention, when the fluorine-based resin has a repeating unit represented by formula (2), from the viewpoint of increasing solubility in a fluorine-based solvent and enabling more efficient photocuring, the fluorine-based resin preferably contains 10 mol % to 70 mol %, more preferably 20 mol % to 50 mol %, and even more preferably 30 mol % to 50 mol % of the repeating unit represented by formula (1).

[0091] The repeating unit represented by formula (2) is preferably contained in an amount of 10 mol % to 70 mol %, more preferably 20 mol % to 60 mol %, and even more preferably 30 mol % to 50 mol %.

[0092] Furthermore, the repeating units containing fluorine atoms are preferably contained in an amount of 10 mol % to 80 mol %, more preferably 10 mol % to 60 mol %, still more preferably 10 mol % to 40 mol %, and even more preferably 10 mol % to 30 mol %.

[0093] The fluororesin according to one embodiment of the present invention may contain other monomer repeating units within the scope of the present invention. Examples of other monomer repeating units include olefin residues such as ethylene residue, propylene residue, and 1-butene residue; vinyl aromatic hydrocarbon residues such as styrene residue and α-methylstyrene residue; vinyl carboxylate ester residues such as vinyl acetate residue, vinyl propionate residue, and vinyl pivalate residue; vinyl ether residues such as methyl vinyl ether residue, ethyl vinyl ether residue, and butyl vinyl ether residue; N-substituted maleimide residues such as N-methylmaleimide residue, N-cyclohexylmaleimide residue, and N-phenylmaleimide residue; acrylonitrile residue; and methacrylonitrile residue.

[0094] The molecular weight of the fluororesin of the present invention is not limited, and may be, for example, 2,000 to 10,000,000 (g / mol). From the viewpoint of the solution viscosity and mechanical strength of the resulting resin, the molecular weight is preferably 10,000 to 1,000,000 (g / mol).

[0095] The method for synthesizing the fluororesin of the present invention is not particularly limited, and the fluororesin can be synthesized, for example, by mixing the monomer that forms the repeating unit B described above, the monomer that forms the repeating unit containing a fluorine atom described above, and a monomer that forms any other repeating unit, and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

[0096] When the fluororesin according to one embodiment of the present invention has a repeating unit represented by formula (2), the synthesis method of the fluororesin is not particularly limited. For example, the fluororesin can be synthesized by mixing a monomer forming the repeating unit B described above, a monomer forming the repeating unit represented by formula (2) described above, a monomer forming the repeating unit containing a fluorine atom described above, and a monomer forming any other repeating unit, and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

[0097] The composition according to one embodiment of the present invention will be described below.

[0098] A composition according to one embodiment of the present invention contains at least one solvent selected from an organic solvent and a fluorine-containing solvent, and a fluorine-containing resin.

[0099] The fluorine-based solvent may be any solvent capable of dissolving the fluorine-based resin of the present invention. By using a fluorine-based solvent as a solvent for dissolving the fluorine-based resin, damage to device components mainly composed of organic substances can be minimized during the production of electronic devices by an all-printing method, allowing the electronic devices to fully exhibit their performance.

[0100] The fluorine atom content of the fluorine-based compound constituting the fluorine-based solvent is 50% by mass to 70% by mass, more preferably 55% by mass to 70% by mass, based on the total mass of the fluorine-based compound. If the fluorine atom content exceeds 70% by mass, the fluorine-based resin described above will not be sufficiently dissolved. If the fluorine atom content is less than 50% by mass, the surface of the organic semiconductor film may be dissolved or swollen when the solvent is applied or printed on the organic semiconductor film.

[0101] As the fluorine-containing solvent contained in the composition of the present invention, the following fluorine-containing hydrocarbons, fluorine-containing ethers or fluorine-containing alcohols can be preferably used, and the following fluorine-containing hydrocarbons or fluorine-containing ethers can be more preferably used.

[0102] Fluorinated hydrocarbons have a low ozone depletion potential and are therefore preferred as the fluorinated solvent contained in the composition of the present invention. In particular, fluorinated hydrocarbons that are linear, branched, or cyclic hydrocarbons having 4 to 8 carbon atoms and in which at least one hydrogen atom has been substituted with a fluorine atom are preferred because they are easy to apply.

[0103] Specific examples of such fluorine-containing hydrocarbons include butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, and benzene in which at least one hydrogen atom has been substituted with a fluorine atom.Specific examples include fluorine-containing hydrocarbons such as 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.

[0104] The boiling point of the fluorine-containing hydrocarbon is preferably not more than 200° C., more preferably not more than 180° C. When the boiling point of the fluorine-containing hydrocarbon is not more than 200° C., the fluorine-containing hydrocarbon can be easily evaporated and removed by heating.

[0105] Among the above-mentioned fluorine-containing hydrocarbons, the following can be given as examples having particularly preferable boiling points.

[0106] 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.

[0107] Furthermore, because of its low ozone depletion potential, a fluorine-containing ether can be used as the fluorine-based solvent. In particular, the boiling point of the fluorine-containing ether is preferably 200° C. or lower, more preferably 180° C. or lower. When the boiling point of the fluorine-containing ether is 200° C. or lower, the fluorine-containing ether can be easily evaporated and removed from the fluorine-based resin film by heating.

[0108] Preferred examples of the fluorine-containing ether 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, and ethyl nonafluorobutyl ether.

[0109] 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-ethoxydodecafluorohexane, (1,1,1,2,3,3-hexafluoropropoxy)pentane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, and methoxyperfluoroheptene.

[0110] A fluorine-containing alcohol can be used as the fluorine-based solvent. The fluorine-containing alcohol used preferably has a boiling point of 200° C. or lower, more preferably 180° C. or lower. When the boiling point of the fluorine-containing alcohol is 200° C. or lower, the fluorine-containing alcohol can be easily evaporated and removed by heating.

[0111] Preferred examples of the fluorine-containing alcohol 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.

[0112] Furthermore, two or more types of fluorine-based solvents may be contained in order to further enhance the solubility of the fluorine-based resin.

[0113] 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 is no limitation on the organic solvent as long as it dissolves the fluorine-based resin of the present invention, and examples thereof include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a mixture of dimethylnaphthalene isomers, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, and the like. Benzyl alcohol, 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 Benzyl alcohol, 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 fluorine-based resins is suitable, and xylene and propylene glycol monomethyl ether acetate are preferred. Mixed solvents containing two or more of the aforementioned solvents in appropriate ratios can also be used.

[0114] A composition of a fluorine-based resin and at least one of an organic solvent and a fluorine-based solvent according to one embodiment of the present invention preferably contains 1 wt % to 50 wt % of the fluorine-based resin and 50 wt % to 99 wt % of the solvent.

[0115] The composition according to one aspect of the present invention may also contain a photosensitizer. The photosensitizer may be any agent that accelerates the crosslinking reaction of the photocrosslinkable group.

[0116] Examples of photosensitizers include acyloins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; carbonyls such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzil; 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; p-toluenesulfonyl chloride, and 1-naphthalene. Examples of suitable photosensitizers 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 biclamide; coumarins such as 7-diethylamino-3-thenoylcoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, bisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; and dyes such as ethionine, thionine, and methylene blue. The addition of a photosensitizer allows the fluororesin of one embodiment of the present invention to be crosslinked (insolubilized) at a lower exposure dose. Furthermore, two or more types of such sensitizers can be used in combination as needed.

[0117] A composition of a fluorine-based resin, a photosensitizer, and at least one of an organic solvent and a fluorine-based solvent according to one aspect of the present invention preferably contains 1 wt % to 50 wt % of the fluorine-based resin, 50 wt % to 99 wt % of the solvent, and 0.001 wt % to 5 wt % of the photosensitizer.

[0118] A pattern according to one aspect of the present invention will be described below.

[0119] The fluororesin of the present invention can be used to form a pattern. More specifically, the fluororesin of the present invention or a composition thereof is used to obtain a photocrosslinked product, and a pattern is formed.

[0120] First, a fluororesin coating film is formed on the surface of a substrate by a known coating film forming method. Examples of the substrate include various glass plates, polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, thermoplastic plastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide, epoxy resins, polyester resins, and thermosetting plastic sheets such as poly(meth)acrylic resins.

[0121] Examples of methods for forming the coating 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, superflexographic printing, screen printing, inkjet printing, letterpress reverse printing, reverse offset printing, and adhesion contrast printing.

[0122] The coating is then dried. This process volatilizes the solvent, resulting in a non-sticky coating. Drying conditions vary depending on the boiling point and blend ratio of the solvent used, but can be broadly adjusted to a temperature of 50 to 150°C and a time of 10 to 2000 seconds.

[0123] When a coating film having a predetermined shape, i.e., the same shape as a desired pattern, is formed using a printing method during coating film formation, exposure to light causes the coating film having the predetermined shape to be photocrosslinked to obtain a photocrosslinked product, which is then fixed, thereby forming a pattern.

[0124] On the other hand, if a coating film having a predetermined shape is not formed during coating film formation, a pattern can be formed from the coating film using photolithography. When using photolithography, the dried coating film is first exposed to light through a mask having a predetermined shape, i.e., a shape that can form the desired pattern, to cause photocrosslinking.

[0125] When the fluororesin of the present invention is cured by photocrosslinking, radiation such as ultraviolet light or visible light is used, for example, ultraviolet light having a wavelength of 245 to 435 nm. The irradiation dose is appropriately changed depending on the composition of the resin, but for example, it is 10 to 5000 mJ / cm. 2 From the viewpoint of preventing a decrease in the degree of crosslinking and improving economic efficiency by shortening the process time, the irradiation dose is preferably 100 to 4000 mJ / cm. 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, and metal halide lamps.

[0126] Irradiation with ultraviolet light is usually carried out in the air, but can also be carried out in an inert gas or under a certain amount of inert gas flow if necessary. If necessary, the photo-crosslinking reaction can be promoted by adding the above-mentioned photosensitizer. The film is then developed with a developer to remove the unexposed areas. The developer may be any solvent that dissolves the uncured fluorine-based resin, such as aromatic solvents such as benzene, toluene, and xylene; ether-based solvents such as dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate; 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.

[0127] The development time is preferably 30 to 300 seconds. The development method may be either a puddle method or a dipping method. After development, the substrate is washed with a solvent and air-dried with compressed air or compressed nitrogen to remove the solvent from the substrate. Subsequently, a pattern is formed by heat treatment using a heating device such as a hot plate or oven, preferably at 40 to 150°C for 5 to 90 minutes.

[0128] After forming a pixel pattern through the photolithography process, contamination on the substrate surface within the pixels may be removed. For example, the substrate surface may be cleaned by irradiating it with short-wavelength ultraviolet light such as a low-pressure mercury lamp or excimer UV, or by photo-ashing treatment. Photo-ashing treatment is a treatment 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.

[0129] Thus, the fluororesin of the present invention is soluble in a fluorine-based solvent or an organic solvent, and upon irradiation with light, the photocrosslinkable groups in the side chains are crosslinked and cured, rendering the fluororesin insoluble in the solvent used. Utilizing this property, the fluororesin of the present invention can be used as a negative resist in which, when crosslinked by irradiation with light, the unirradiated portions are removed by the fluorine-based solvent or the organic solvent.

[0130] After patterning using the fluororesin of the present invention, the portion where the fluororesin remains after crosslinking (outside the pattern) preferably has a contact angle with the ink of 40° or more, more preferably 50° or more, to prevent the ink from wetting and spreading to form the functional layer.

[0131] The fluororesin of the present invention can be made into a protective film by the same methods as those for forming a pattern, such as coating film formation, photocrosslinking, and development.

[0132] The fluorine-based resin of the present invention has excellent liquid repellency and can be used as a pattern material in the production of organic transistor elements, color filters, and organic EL elements. The fluorine-based resin of the present invention can also be used in electronic devices including the organic transistor elements, color filters, and organic EL elements.

[0133] The electronic device according to one embodiment of the present invention will be described in detail below.

[0134] The fluororesin of the present invention can be used in electronic devices, and more specifically, can be used in electronic devices comprising a photocrosslinked product of the fluororesin of the present invention or a composition containing the fluororesin and at least one of an organic solvent and a fluorine-containing solvent, and examples of the electronic device include organic transistors.

[0135] A typical organic transistor has a gate insulating layer on a substrate, and is obtained by further depositing an organic semiconductor layer on this gate insulating layer, followed by the formation of a source electrode, a drain electrode, and a gate electrode. An example of an organic transistor device structure is shown in cross section in Figure 1. 1001 denotes a bottom gate-top contact type, 1002 a bottom gate-bottom contact type, 1003 a top gate-top contact type, and 1004 a top gate-bottom contact type device structure. 1 denotes the organic semiconductor layer, 2 a substrate, 3 a gate electrode, 4 a gate insulating layer, 5 a source electrode, and 6 a drain electrode.

[0136] One embodiment of the organic transistor of the present invention is shown in Figure 2. The organic transistor 1005 shown in Figure 2 corresponds to the bottom gate-bottom contact type in Figure 1. 7 indicates a pattern, and 8 indicates a protective film layer.

[0137] The substrate that can be used in the organic transistor is not particularly limited as long as it can ensure sufficient flatness for fabricating an element, and examples thereof 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; surface-coated nonwoven fabric; and the like. Composite materials made of these materials or multilayer materials of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

[0138] Examples of plastics that can be used as substrates include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefins, fluorinated cyclic polyolefins, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomers, polyurethane elastomers, polyolefin elastomers, polyamide elastomers, and styrene block copolymers. Furthermore, two or more of the above plastics can be laminated together to form a substrate.

[0139] There are no limitations on the organic semiconductor that can be used in the organic semiconductor layer, and both N-type and P-type organic semiconductors can be used, and a bipolar transistor combining N-type and P-type can also be used. Also, both low-molecular-weight and high-molecular-weight organic semiconductors can be used, and they can also be used in combination. Specific examples of organic semiconductor compounds include compounds represented by the following formulas (D-1) to (D-11). [ka] [ka] [ka] [ka] In the present invention, examples of methods for forming an organic semiconductor layer include a method of vacuum vapor deposition of an organic semiconductor, or a method of dissolving an organic semiconductor in an organic solvent and coating or printing the solution, but there are no limitations as long as the method can form a thin film of an organic semiconductor layer. When coating or printing using a solution in which the organic semiconductor layer is dissolved in an organic solvent, the concentration of the solution 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 layer thickness, it is preferably 0.5% to 5 wt%. The organic solvent used in this case is not limited as long as it dissolves the organic semiconductor at a certain concentration that allows film formation, and examples thereof include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a mixture of dimethylnaphthalene isomers, 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, 3-methyl-4-phenylpropanol, 2-methyl-1, ... -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 crystal film with desirable properties, a solvent with a high dissolving power for the organic semiconductor and a boiling point of 100°C or higher is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. Mixed solvents containing two or more of the above solvents in appropriate proportions can also be used.

[0140] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles, can be added to the organic semiconductor layer as needed, either as solids or as dispersions of nanoparticles in water or organic solvents, and a protective film can be formed by coating the insulating layer with the polymer solution. Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied to this protective film as needed.

[0141] Examples of gate electrodes, source electrodes, or drain electrodes that can be used 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, as well as organic electrodes such as doped conductive polymers (e.g., PEDOT-PSS). Multiple layers of these conductive materials can also be used. Furthermore, to improve carrier injection efficiency, these electrodes can be surface-treated using a surface treatment agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

[0142] Furthermore, there are no particular limitations on the method for forming an electrode on the substrate, insulating layer, or organic semiconductor layer, and examples thereof include vapor deposition, high-frequency sputtering, and electron beam sputtering. It is also possible to employ methods such as solution spin coating, drop casting, dip coating, doctor blade coating, die coating, pad printing, roll coating, gravure printing, flexographic printing, superflexographic printing, screen printing, inkjet printing, and letterpress reverse printing using an ink in which nanoparticles of the conductive material are dissolved in water or an organic solvent.

[0143] The fluorine-containing resin of the present invention can be suitably used for patterns and protective film layers in organic transistors.

[0144] From the viewpoint of practicality of the organic transistor element, the organic transistor according to one aspect of the present invention has a mobility of 0.20 cm 2 It is preferable that the value is equal to or greater than / Vs.

[0145] From the viewpoint of practicality of the organic transistor element, the organic transistor according to one aspect of the present invention has an on-current / off-current ratio of 10 5 It is preferable that this is equal to or greater than this.

[0146] From the perspective of the practicality of the organic transistor device, it is preferable that there is no hysteresis in the current between the source and drain in the organic transistor according to one aspect of the present invention.

Example

[0147] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0148] In the examples, the following conditions and equipment were used.

[0149] <Monomer purity> Gas chromatography apparatus; manufactured by Shimadzu Corporation, (trade name) GC2014 Column; manufactured by RESTEK Corporation, (trade name) Rxi-1HT, 30m Using the above gas chromatography apparatus (GC), the purity of the monomer was analyzed.

[0150] <Composition of fluororesin> Using a nuclear magnetic resonance measurement apparatus (manufactured by JEOL Ltd., trade name JNM-ECZ400S), proton nuclear magnetic resonance spectroscopy ( 1 H-NMR) spectrum analysis was used to determine it.

[0151] <Spin coating> MS-A100 manufactured by Mikasa Co., Ltd. was used.

[0152] <Film thickness measurement> Measurement was performed using a DektakXT stylus profiler manufactured by Bruker Corporation.

[0153] <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.

[0154] <Inkjet printing> A solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) synthesized according to the manufacturing method described in JP 2015-224238 A was filled into a cartridge with a basic droplet volume of 10 pL, and printed using an inkjet device (Fujifilm Dimatix, DMP-2831, stage temperature 30°C, cartridge temperature 30°C).

[0155] <Laser microscope> The inkjet-printed organic semiconductor layer or pattern was confirmed using a laser microscope, OPTELICS HYBRID, manufactured by Lasertec Corporation.

[0156] In the examples, the following results were obtained:

[0157] Synthesis Example 1 (Synthesis of Photocrosslinkable Monomer 1) Under a nitrogen atmosphere, 6 g of glycerin monomethacrylate (Blenmer GLM, NOF Corp.), 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 acid chloride and 42 g of tetrahydrofuran were placed in a glass bottle and dissolved. Then, nitrogen was passed through the flask containing glycerin monomethacrylate, triethylamine, and tetrahydrofuran, and the cinnamic acid chloride solution was added dropwise using a dropping funnel and stirred for 22 hours. The by-product salt was then removed by filtration, and the tetrahydrofuran was removed using an aspirator. The product was then dissolved in 50 g of toluene, washed three times with aqueous sodium bicarbonate solution, and vacuum dried. The substance obtained after drying was 1 H-NMR and gas chromatography analysis confirmed that the compound was a substance (photocrosslinkable monomer 1) represented by the following formula (7) (GC purity 87%). (Photo-crosslinkable monomer 1) [ka] Example 1 (Polymerization of Fluorine-Based Resin 1) A 75 mL glass ampoule was charged with 6.78 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 9.10 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.27 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 37 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 13.8 g of fluororesin 1 (yield: approximately 87%). 1 H-NMR measurement confirmed that the composition was 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 %), and that it was a copolymer represented by formula (8). 1 The results of H-NMR measurement are shown in Figure 3.

[0158] (Fluorine-based resin 1) [ka] Synthesis Example 2 (Synthesis of Photocrosslinkable Monomer 2) Under a nitrogen atmosphere, 5 g of 4-chlorocinnamic acid, 7 g of thionyl chloride, 3 drops of N,N-dimethylformamide, and 20 ml of dichloromethane were added to a 50 mL Schlenk tube. The reaction was carried out at 40°C with stirring for 4 hours, and the mixture was then dried under vacuum to obtain 4-chlorocinnamic acid chloride. Subsequently, under a nitrogen atmosphere, 1.7 g of glycerin monomethacrylate (Blenmer GLM, NOF Corp.), 3 g of triethylamine, and 5.1 g of toluene were placed in a 100 mL flask and thoroughly mixed. Under a nitrogen atmosphere, 5.3 g of 4-chlorocinnamic acid chloride and 16 g of toluene were dissolved in a glass bottle. Nitrogen was then purged into the flask containing glycerin monomethacrylate, triethylamine, and toluene, and a solution of pCl-cinnamic acid chloride was added dropwise using a dropping funnel. The mixture was then stirred for 22 hours. The by-product salt was then removed by filtration. The mixture was then washed three times with aqueous sodium bicarbonate solution and dried under vacuum. The resulting material after drying was 1 H-NMR and gas chromatography analysis confirmed that the compound was a compound (photocrosslinkable monomer 2) represented by the following formula (9) (GC purity 93%). (Photo-crosslinkable monomer 2) [ka] Example 2 (Polymerization of Fluorine-Based Resin 2) A 75 mL glass ampoule was charged with 2.31 g of the photocrosslinkable monomer 2 obtained in Synthesis Example 2, 2.85 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.09 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 12 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule and precipitated by dropping it into 200 mL of methanol. The polymer solution was then washed twice with 100 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 3.0 g of fluororesin 2 (yield: approximately 61%). 1H-NMR measurement confirmed that the composition was photocrosslinkable monomer 2 (photocrosslinking group unit 2) [B-13] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 36 / 64 (mol %), and that it was a copolymer represented by formula (10).

[0159] (Fluorine-based resin 2) [ka] Synthesis Example 3 (Synthesis of Photocrosslinkable Monomer 3) Synthesis was carried out in the same manner as in Synthesis Example 2, except that (E)-3-(4-methylphenyl)-2-propenoic acid was used instead of 4-chlorocinnamic acid. Analysis confirmed that the obtained substance was a compound (photocrosslinkable monomer 3) represented by the following formula (11). (GC purity: 89%) (Photo-crosslinkable monomer 3) [ka] Example 3 (Polymerization of Fluorine-Based Resin 3) A 75 mL glass ampoule was charged with 2.30 g of the photocrosslinkable monomer 3 obtained in Synthesis Example 3, 2.95 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.09 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 12 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule and precipitated by dropping it into 200 mL of methanol. The polymer solution was then washed twice with 100 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 4.2 g of fluororesin 3 (yield: approximately 84%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 3 (photocrosslinking group unit 3) [B-2] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 37 / 63 (mol %), and that it was a copolymer represented by formula (12).

[0160] (Fluorine-based resin 3) [ka] Synthesis Example 4 (Synthesis of Photocrosslinkable Monomer 4) Synthesis was carried out in the same manner as in Synthesis Example 2, except that 3-(trifluoromethyl)cinnamic acid was used instead of 4-chlorocinnamic acid. Analysis confirmed that the obtained substance was a compound (photocrosslinkable monomer 4) represented by the following formula (13). (GC purity: 81%) (Photo-crosslinkable monomer 4) [ka] Example 4 (Polymerization of Fluorine-Based Resin 4) A 75 mL glass ampoule was charged with 2.78 g of the photocrosslinkable monomer 4 obtained in Synthesis Example 4, 2.69 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.08 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 13 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule and precipitated by dropping it into 200 mL of methanol. The polymer solution was then washed twice with 100 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 4.1 g of fluororesin 4 (yield: approximately 82%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 4 (photocrosslinking group unit 4) [B-16] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 37 / 63 (mol %), and that it was a copolymer represented by formula (14).

[0161] (Fluorine-based resin 4) [ka] Example 5 (Polymerization of Fluorine-Based Resin 5) A 75 mL glass ampoule was charged with 5.4 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 5.4 g of 1H,1H,2H,2H-nonafluorohexyl methacrylate, 0.21 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 25 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 8.4 g of fluororesin 5 (yield: approximately 83%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-nonafluorohexyl methacrylate (fluorine-based unit 2) [C-27] = 39 / 61 (mol %), and that it was a copolymer represented by formula (15).

[0162] (Fluorine-based resin 5) [ka] Example 6 (Polymerization of Fluorine-Based Resin 6) A 75 mL glass ampoule was charged with 6.6 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 4.4 g of 2,2,3,3,3-pentafluoropropyl methacrylate, 0.26 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 25 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 7.0 g of fluororesin 6 (yield: approximately 69%). 1H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 2,2,3,3,3-pentafluoropropyl methacrylate (fluorine-based unit 3) [C-25] = 39 / 61 (mol %), and that it was a copolymer represented by formula (16).

[0163] (Fluorine-based resin 6) [ka] Example 7 (Polymerization of Fluorine-Based Resin 7) A 75 mL glass ampoule was charged with 5.7 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 5.2 g of 1H,1H,5H-octafluoropentyl methacrylate, 0.22 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 25 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 4.3 g of fluororesin 7 (yield: approximately 43%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,5H-octafluoropentyl methacrylate (fluorine-based unit 4) [C-23] = 40 / 60 (mol %), and that it was a copolymer represented by formula (17).

[0164] (Fluorine-based resin 7) [ka] Example 8 (Polymerization of Fluorine-Based Resin 8) A 75 mL glass ampoule was charged with 4.8 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 5.9 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 0.19 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 25 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was completed, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 0.8 g of fluororesin 8 (yield: approximately 8%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate (fluorine-based unit 5) [C-24] = 41 / 59 (mol %), and that it was a copolymer represented by formula (18).

[0165] (Fluorine-based resin 8) [ka] Example 9 (Polymerization of Fluorine-Based Resin 9) A 75 mL glass ampoule was charged with 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 Perhexyl ND (NOF Corp.) as a polymerization initiator, and 26 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 8.8 g of fluororesin 9 (yield: approximately 88%). 1H-NMR measurement confirmed that the composition was 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 %), and that it was a copolymer represented by formula (19).

[0166] (Fluorine-based resin 9) [ka] Example 10 (Polymerization of Fluorine-Based Resin 10) A 75 mL glass ampoule was charged with 10.6 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.0 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.18 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 27 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 8.2 g of fluororesin 10 (yield: approximately 82%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 15 / 85 (mol %), and that it was a copolymer represented by formula (20).

[0167] (Fluorine-based resin 10) [ka] Example 11 (Production of Fluorine-Based Resin 11) A 15 mL glass ampoule was charged with 0.81 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.35 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.16 g of methyl methacrylate, 0.03 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 3.1 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was completed, the polymer solution was removed from the ampoule and precipitated by dropping it into 100 mL of methanol. The polymer solution was then washed twice with 100 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 1.1 g of fluororesin 11 (yield: approximately 83%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] / methyl methacrylate (non-fluorine-based unit) = 36 / 22 / 42 (mol %), and that it was a copolymer represented by the following formula (21).

[0168] (Fluorine-based resin 11) [ka] Synthesis Example 5 (Synthesis of Photocrosslinkable Monomer 5) Synthesis was carried out in the same manner as in Synthesis Example 2, except that 4-(trifluoromethyl)cinnamic acid was used instead of 4-chlorocinnamic acid. Analysis confirmed that the obtained substance was a compound (photocrosslinkable monomer 5) represented by the following formula (22). (GC purity: 83%) (Photocrosslinkable monomer 5) [ka] Example 12 (Polymerization of Fluorine-Based Resin 12) A 75 mL glass ampoule was charged with 2.69 g of the photocrosslinkable monomer 5 obtained in Synthesis Example 5, 2.78 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.08 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 13 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was completed, the polymer solution was removed from the ampoule and precipitated by dropping it into 200 mL of methanol. The polymer solution was then washed twice with 100 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 4.1 g of fluororesin 12 (yield: approximately 83%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 5 (photocrosslinking group unit 5) [B-15] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 36 / 64 (mol %), and that it was a copolymer represented by formula (23).

[0169] (Fluorine-based resin 12) [ka] Comparative Example 1 (Polymerization of non-fluorine-based resin 1) A 75 mL glass ampoule was charged with 4.36 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.32 g of methyl methacrylate, 0.17 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 13 g of 2-butanone. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization to occur. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol, followed by washing twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 4.6 g of non-fluorinated resin 1 (yield: approximately 81%). 1H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) / methyl methacrylate (non-fluorine-based unit) = 38 / 62 (mol %), and that it was a copolymer represented by the following formula (24).

[0170] (Non-fluorinated resin 1) [ka] Synthesis Example 6 (Synthesis of Photocrosslinkable Monomer 6) Under a nitrogen atmosphere, 6 g of 2-hydroxyethyl methacrylate, 5.3 g of triethylamine, and 18 g of tetrahydrofuran were placed in a 200 mL flask and thoroughly mixed. Also, under a nitrogen atmosphere, 8.7 g of cinnamic acid chloride and 26 g of tetrahydrofuran were placed in a glass bottle and dissolved. Then, nitrogen was passed through the flask containing 2-hydroxyethyl methacrylate, triethylamine, and tetrahydrofuran, and the cinnamic acid chloride solution was added dropwise using a dropping funnel and stirred for 22 hours. The by-product salt was then removed by filtration, and the tetrahydrofuran was removed using an aspirator. The product was then dissolved in 50 g of toluene, washed three times with aqueous sodium bicarbonate solution, and vacuum dried. After drying, the obtained substance 1 H-NMR and gas chromatography confirmed that the compound was a substance (photocrosslinkable monomer 6) represented by the following formula (25). (GC purity: 91%)

[0171] (Photo-crosslinkable monomer 6) [ka] Comparative Example 2 (polymerization production of fluorine-based resin 13) A 75 mL glass ampoule was charged with 3.11 g of the photocrosslinkable monomer 2 obtained in Synthesis Example 2, 7.14 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 0.21 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 24 g of 2-butanone. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule and precipitated by dropping it into 500 mL of methanol. The polymer solution was then washed twice with 300 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 9.2 g of fluororesin 13 (yield: approximately 90%). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 6 (photocrosslinking group unit 6) / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit) = 38 / 62 (mol %), and that it was a copolymer represented by the following formula (26).

[0172] (Fluorine-based resin 13) [ka] <Evaluation of solubility in fluorinated solvents> The synthesized fluororesins 1 to 12 or non-fluororesin 1 were added to each of the following fluorosolvents (solvents 1 to 8) at a concentration of 3 wt %, and mixed while heating to 50°C. The temperature was then lowered to room temperature, and the presence of insoluble or precipitated matter was visually confirmed. The results are shown in Table 1. In Table 1, the presence of insoluble or precipitated matter is indicated as "insoluble," and the absence of these is indicated as "soluble." Solvent 1: 2H,3H-decafluoropentane Solvent 2: 1,1,2,2,3,3,4-heptafluorocyclopentane Solvent 3: 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether Solvent 4: Hexafluorobenzene Solvent 5: 2,2,3,3-tetrafluoro-1-propanol Solvent 6: 2,2,3,3,4,4,5,5-octafluoro-1-pentanol Solvent 7: 1H,1H,7H-dodecafluoro-1-heptanol Solvent 8: 2,2,3,3,4,4,4-heptafluoro-1-butanol It was confirmed that fluorine-based resins 1 to 12 were soluble in many fluorine-based solvents. [Table 1] <Evaluation of liquid repellency (water repellency and oil repellency)> Washed and dried 30 x 30 mm 2 A solution of fluorine-based resins 1 to 11 or non-fluorine-based resin 1 (3 wt%, solvent: propylene glycol monomethyl ether acetate) was spin-coated onto glass (Corning EagleXG) at 500 rpm for 5 seconds and 1500 rpm for 20 seconds. When UV irradiation was performed, the intensity was 500 mJ / cm. 2 The contact angles with water, diiodomethane, m-xylene, and tetralin were measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name DM-300) by the θ / 2 method. The results are shown in Table 2.

[0173] It was confirmed that fluorine-based resins 1 to 12 had excellent liquid repellency, whereas non-fluorine-based resin 1 did not have excellent liquid repellency. [Table 2] <Evaluation of photocrosslinking (curing) properties> Washed and dried 30 x 30 mm 2 A solution of fluororesin 1 to 11 or fluororesin 13 or a solution further containing a sensitizer (see Table 3 for the solutions used) was spin-coated onto a glass substrate (Corning Eagle XG) using a spin coater so that the film thickness after drying would be 100 to 150 nm, and the substrate was thoroughly dried. 2The resin film was photocrosslinked by irradiating it with ultraviolet light. The thickness of this film was measured using a Bruker DektakXT stylus profiler and designated as T0. Next, the glass plate coated with this photocrosslinked resin film was immersed in acetone, a good solvent for fluororesins, for 1 minute, then removed and dried at 100°C on a hot plate for 1 minute, after which the film thickness was measured and designated as T1. Using these film thickness measurements, the remaining film ratio (R) was calculated using the following formula:

[0174] R = T1 / T0 x 100(%) The photocrosslinking (curing) property was evaluated using a residual film rate (R) of 95% or more as the criterion for crosslinking. The lower the UV irradiation dose required to achieve a residual film rate of 95% or more, the higher (faster) the photocrosslinking property. 2 The UV irradiation dose below 500mJ / cm2 is judged as "crosslinking" when R95% or more is achieved. 2 At the following UV irradiation doses, those that did not achieve R95% or more were judged to be "insufficiently crosslinked." The results are shown in Table 3: Solvent 6: 2,2,3,3,4,4,5,5-octafluoro-1-pentanol Solvent 9: Propylene glycol monomethyl ether acetate Sensitizer 1: 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Co., Ltd.). [Table 3] <Pattern formation and evaluation of semiconductor solution coating> For pattern formation, fluorine-based resins 1 to 11 or non-fluorine-based resin 1 were dissolved in propylene glycol monomethyl ether acetate solvent to prepare a 3 wt% solution. The mask used for pattern formation was a chrome-patterned mask with a shape of 10 vertical and 10 horizontal squares with sides of 50 μm. 2 The solution was spin-coated onto a glass substrate, and a mask was placed on the film obtained. UV was then applied at 300 mJ / cm. 2 After irradiation, the uncrosslinked portions were removed by washing with acetone for 1 minute, and a 50 × 50 μm 2A laser microscope was used to check whether a pattern with 100 holes of the same size had been formed.

[0175] Next, the semiconductor solution was evaluated for its separate application. A 0.8 wt % tetralin solution of the organic semiconductor (di-n-hexyldithienobenzodithiophene) represented by the above formula (D-11) was inkjet-printed inside the pattern (the area where fluorine-based resins 1 to 11 or non-fluorine-based resin 1 had been removed; the same applies below). After printing, a laser microscope was used to confirm whether the semiconductor solution had not wetted the outside of the pattern (the area where fluorine-based resins 1 to 11 or non-fluorine-based resin 1 had not been removed) and whether a semiconductor layer had been formed inside the pattern. The results are shown in Table 4. The organic semiconductor represented by formula (D-11) was synthesized according to the method described in JP 2012-209329 A. [Table 4] <Evaluation of organic transistors> (Gate electrode formation) 100×100mm 2 The glass substrate was placed in a sputtering apparatus (Shibaura Mechatronics Corporation, CFS-4EP-LL), and a silver film was formed to a thickness of 50 nm, which was then patterned by photolithography to form a silver electrode, that is, a gate electrode.

[0176] (Formation of insulating layer) On the substrate on which the gate electrode was formed, an insulating layer was formed using a parylene deposition apparatus (PDS2010, Japan Parylene LLC) so that the film thickness of parylene C was about 500 nm.

[0177] (Formation of source and drain electrodes) The substrate with the insulating layer formed above was placed in a sputtering apparatus, and a silver film was deposited to a thickness of 50 nm at 200 W. It was then patterned by photolithography to form source and drain electrodes with a channel length of 20 μm and a channel width of 50 μm.

[0178] (Lydope-repellent pattern formation) A 2-methoxy-1-methylethyl acetate solution (3 wt%) of each of the fluororesins 1 to 11 was prepared and spin-coated onto a substrate on which source and drain electrodes had been formed to a film thickness of approximately 100 nm, and then dried at 100°C for 1 minute. After that, a mask with a rectangular light-shielding area of ​​30 μm × 60 μm was aligned so that the center of the light-shielding area coincided with the center between the source and drain electrodes, and then brought into contact with the substrate and irradiated with 250 mJ / cm 2 The area other than the light-shielding area was crosslinked by irradiating the substrate with ultraviolet light of 1000 kJ / s. After the UV irradiation, the substrate was washed with acetone for 1 minute and then blown dry with nitrogen gas to remove the fluorine-based resin present in the light-shielding area of ​​the mask, thereby forming a liquid-repellent pattern.

[0179] (electrode surface modification) The substrate on which the source and drain electrodes were formed was immersed in an isopropyl alcohol solution of pentafluorobenzenethiol (30 mmol / L) for 5 minutes to modify the surface of the electrodes formed on the substrate.

[0180] (Preparation of solution for forming organic semiconductor layer) Under air, 24 mg of the organic semiconductor represented by the above formula (D-11) (di-n-hexyldithienobenzodithiophene), 3 mg of polystyrene (Sigma-Aldrich, average Mw 280,000), and 2,973 mg of tetralin (Sigma-Aldrich) were placed in a 10 ml sample tube, and heated to 50°C to dissolve the organic semiconductor and polystyrene, thereby preparing a solution for forming an organic semiconductor layer. The organic semiconductor represented by formula (D-11) was synthesized according to the method described in JP 2012-209329 A.

[0181] (Formation of organic semiconductor layer) The organic semiconductor layer-forming solution prepared above was filled into a cartridge with a basic droplet volume of 10 pL, and printed onto the channel portion between the electrode-modified source and drain electrodes using an inkjet device (Fujifilm Dimatix, DMP-2831). The organic semiconductor layer was then formed by drying on a hot plate at 90°C for 10 minutes, and an organic transistor was fabricated.

[0182] (Electrical characteristics results) The gate voltage (Vg) of the fabricated organic transistor was scanned with a source-drain voltage (Vd) of -15 V, and the transfer characteristics (Id-Vg) before applying the bias voltage were measured. The mobility was found to be 0.5-0.7 cm. 2 / V·s, demonstrating excellent mobility.

[0183] <Damage evaluation of organic semiconductors> Fluorine-based resin 1 obtained in Example 1 was added with 4,4'-bis(diethylamino)benzophenone as a sensitizer, and the mixture was dissolved in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solvent to prepare a solution (fluorine-based resin 15 wt%, sensitizer 0.4 wt%). The solution was spin-coated onto the organic semiconductor layer of the organic transistor to form a protective film of approximately 2 μm. Thereafter, a mask having a light-shielding portion was brought into contact with the substrate on which the protective film had been formed, and 300 mJ / cm 2 The mask was then cured by irradiating it with ultraviolet light. The fluorine-based resin present in the light-shielding areas of the mask was then removed using 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, a fluorine-based solvent, to form a pattern. The results showed that the change in mobility before and after the formation of the protective film was less than 5%, and there was no damage to the organic semiconductor. [Explanation of symbols]

[0184] 1. Organic semiconductor layer 2 boards 3. Gate electrode 4 Gate insulating layer 5. Source electrode 6 Drain electrode 7 patterns 8 Protective film layer

Claims

1. A fluororesin having a repeating unit represented by the following formula (1) containing a photocrosslinkable group and a repeating unit containing a fluorine atom: 【Chemical 1】 (In formula (1), R １ represents a hydrogen atom or a methyl group, L １ represents a single bond or a divalent linking group, A represents an m-valent linking group, R ２ , R ３ , R ４ , R ５ and R ６ 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 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 equal to m-1.

2. The fluorine-containing resin according to claim 1, further comprising a repeating unit represented by the following formula (2): 【Chemistry 2】 (In formula (2), R ７ represents a hydrogen atom or a methyl group, and R8 represents an alkyl group having 1 to 30 carbon atoms.

3. 3. The fluorine-based resin according to claim 1, wherein the repeating unit containing a fluorine atom is a repeating unit represented by the following formula (3): 【Chemistry 3】 (In formula (3), R ９ represents a hydrogen atom or a methyl group. ２ represents a single bond or a divalent linking group, Rf １ 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.

4. The fluorine-containing resin according to any one of claims 1 to 3, wherein in the formula (1), A is one kind of linking group selected from the group consisting of the following formulas (a-1) to (a-4): 【Chemistry 4】 (In formulas (a-1) to (a-4), *L represents L in formula (1) １ The * before the carbon atom represents the bonding position with the oxygen atom constituting the ester group in formula (1).

5. 5. The fluorine-containing resin according to claim 4, wherein in the formula (1), A is a linking group of the formula (a-1).

6. The fluorine-containing resin according to any one of claims 1 to 5, which is soluble in a fluorine-containing solvent.

7. A composition comprising the fluorine-based resin according to any one of claims 1 to 6 and at least one solvent selected from the group consisting of an organic solvent and a fluorine-based solvent.

8. A photocrosslinked product of the fluororesin according to any one of claims 1 to 6 or the composition according to claim 7.

9. A pattern formed from the photocrosslinked product according to claim 8.

10. An electronic device comprising the photocrosslinked product according to claim 8.

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