Fluorine-based resin, composition, photocrosslinking material, and electronic device provided with the same

Abstract

The present application provides a fluorine-based resin having liquid repellency, high solubility to fluorine-based solvents, and insolubilization in a solvent by photocrosslinking at a low exposure amount. The fluorine-based resin of the present application has a repeating unit represented by formula (1) containing a photocrosslinkable group and a repeating unit containing a fluorine atom. (In the formula, R1 represents hydrogen or a methyl group, L1 represents a single bond or a linking group, A represents a linking group, and R2 to R6 represent one selected from the group consisting of hydrogen, a halogen, an alkyl group, a halogenated alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and an amino group.)

Description

TECHNICAL FIELD

[0001] The present application relates to a fluorine-based resin. More specifically, the present application relates to a fluorine-based resin that is suitable for use in electronic devices. BACKGROUND

[0002] In recent years, technical development relating to the production of organic electronic devices based on a full-printing method that is low in cost and high in productivity is being actively pursued. As electronic devices, development of, for example, organic transistors is also being pursued. The organic transistors are produced through a plurality of processes, and include a process in which a protective film composed of a resin protects the organic transistor, and a pattern of an EL light-emitting portion is formed. For example, the pattern is provided so as to cover a source electrode, a drain electrode, and an organic semiconductor layer or a polymer layer, and is not present on an electrode that forms the EL light-emitting portion.

[0003] Generally, the EL light-emitting portion is formed using a photolithography method, which is a technique in which a substrate surface on which a photosensitive substance (resist) is applied is exposed to a pattern via a photomask or an intermediate mask, and a pattern composed of an exposed portion and an unexposed portion is formed. In the photolithography method, the EL light-emitting portion is opened by a dry etching method or a wet etching method.

[0004] As a pattern-forming material, a high-molecular material that is photo-reactive is used. In a coating method such as a full-printing method, the material is applied in an ink form in which the material is dissolved in a solvent, and after the solvent is removed by drying, the material is rendered insoluble in the solvent by causing the material to undergo a photo-crosslinking reaction, and a pattern is formed. Therefore, for the high-molecular material used in a coating method such as a full-printing method, it is required to have both excellent solubility of the material in a solvent, and a property in which the photo-crosslinking reaction of the material can be performed by exposure to ordinary temperature and a short period of time after the solvent is removed.

[0005] Here, a method for producing an organic electroluminescent element included in an organic electroluminescent display and an organic electroluminescent lighting, and the like is shown. First, the above-described high-molecular material is applied to a substrate, and a portion in which a pattern is desired to be formed is caused to undergo a photo-crosslinking reaction, and a portion in which the photo-crosslinking reaction is not performed is removed. Thereby, the remaining portion becomes a pattern. Various functional layers are layered on the portion in which the high-molecular material is removed (inside the pattern). The technique in which the functional layers are formed using an ink-like raw material is promising, but from the viewpoint of preventing the ink from adhering to the inside of the pattern, and preventing the ink from leaking to an area outside the portion in which the high-molecular material is not removed (outside the pattern), it is desired that the material that constitutes the pattern has a liquid-repellent property.

[0006] In addition, in an organic semiconductor element, when an interlayer insulating film or a gate insulating film is formed on a source electrode, a drain electrode, and an organic semiconductor layer, it is desired that the pattern is formed without damage by a photolithography method, and a contact hole or the like is formed on the insulating film.

[0007] As such a material, a negative photosensitive resin composition of Patent Literature 1, which is high in photoreactivity, capable of patterning, and capable of forming a coating film excellent in high dielectric properties, and a photocured pattern manufactured therefrom can be given. However, the resin requires use of water or an organic solvent at the time of development. In addition, the solvent of the composition requires use of an organic solvent such as PGMEA (propylene glycol monomethyl ether acetate). Both the organic solvent and water are causes of reduction in performance of electronic devices. Therefore, in order to prevent reduction in performance of electronic devices, development of a material capable of using a fluorine-based solvent as a solvent is required.

[0008] As such a technique, there is a method of forming a pattern using a fluorine-based resin soluble in a fluorine-based solvent disclosed in Patent Literature 2 and Non-Patent Literature 1. However, the fluorine-based resin has a problem that photo-crosslinking does not occur.

[0009] As a fluorine-based resin that is dissolved in a fluorine-based solvent and subjected to photo-crosslinking, a fluorine-based resin using an anthracene crosslinking group such as that of Non-Patent Literature 2 can be given.

[0010] Prior Art Documents

[0011] Patent Literature

[0012] Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-167513

[0013] Patent Literature 2: Japanese Patent No. 6281427

[0014] Non-Patent Literature

[0015] Non-Patent Literature 1: Appl. Phys. Express 7, 101602 (2014)

[0016] Non-Patent Literature 2: J Polym Sci Polym Chem 53, 1252 (2015) SUMMARY

[0017] PROBLEMS TO BE SOLVED BY THE INVENTION

[0018] However, the fluorine-based resin described in Non-Patent Literature 2 is low in photo-crosslinkability, and requires a high exposure amount. Therefore, a fluorine-based resin having high photoreactivity is required.

[0019] The present application was achieved in view of the above-described technical problems, and aims to provide a fluorine-based resin having liquid repellency, high solubility in a fluorine-based solvent, and capable of being insolubilized in a solvent by photo-crosslinking at a low exposure amount.

[0020] TECHNICAL SOLUTION FOR SOLVING THE PROBLEMS

[0021] The present inventors have conducted intensive studies in order to solve the above-described technical problems, and as a result, have found that a fluorine-based resin having a specific structure can solve the above-described technical problems, thereby completing the present invention.

[0022] That is, the present invention is a fluorine-based resin having a repeating unit represented by the following formula (1) including a photo-crosslinkable group and a repeating unit including a fluorine atom.

[0023] That is, the present invention includes the following technical solutions.

[0024] [1] A fluorine-based resin having a repeating unit represented by the following formula (1) including a photo-crosslinkable group and a repeating unit including a fluorine atom.

[0025] [Chemical Formula 1]

[0026]

[0027] (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, which are the same or different, represent one selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 3 or more, and n represents an integer of m-1.)

[0028] [2] The fluorine-based resin according to [1], further having a repeating unit represented by the following formula (2).

[0029] [Chemical Formula 2]

[0030]

[0031] (In formula (2), R7 represents a hydrogen atom or a methyl group, and R8 represents an alkyl group having 1 to 30 carbon atoms.)

[0032] [3] The fluorine-based resin according to [1] or [2], wherein the repeating unit including a fluorine atom is a repeating unit represented by the following formula (3).

[0033] [Chemical Formula 3]

[0034]

[0035] (In formula (3), R9 represents a hydrogen atom or a methyl group. L2 represents a single bond or a divalent linking group, and Rf1 represents one of the following groups: a straight-chain fluoroalkyl group with 1 to 15 carbon atoms, a branched fluoroalkyl group with 3 to 15 carbon atoms, or a cyclic fluoroalkyl group with 3 to 15 carbon atoms.)

[0036] [4] A fluorinated resin according to any one of [1] to [3], wherein, in the above formula (1), A is a linking group from the group consisting of the following formulas (a-1) to (a-4).

[0037] [Chemistry 4]

[0038]

[0039] (In formulas (a-1) to (a-4), *L represents the bonding position with L1 in formula (1) above, and the * in front of the carbon atom represents the bonding position with the oxygen atom that constitutes the ester group in formula (1) above.)

[0040] [5] According to the fluorinated resin described in [4], in the above formula (1), A is the linking group of the formula (a-1).

[0041] [6] The fluorinated resin according to any one of [1] to [5], wherein the fluorinated resin is soluble in a fluorinated solvent.

[0042] [7] A composition comprising any one of [1] to [6] a fluorinated resin and at least one solvent selected from organic solvents and fluorinated solvents.

[0043] [8] A photocrosslinker, which is a photocrosslinker of any one of the fluorine resins in [1] to [6] or the composition described in [7].

[0044] [9] A pattern consisting of the photocrosslinker described in [8].

[0045]

[10] An electronic device comprising the photocrosslinker described in [8].

[0046] Invention Effects

[0047] According to the present invention, a fluorinated resin exhibiting liquid-repellent properties, high solubility in fluorinated solvents, and insolubility in solvents through photocrosslinking with low exposure can be obtained. This fluorinated resin can be used for patterning, and by using this fluorinated resin for patterning, performance degradation of the resulting electronic device can be prevented. Attached Figure Description

[0048] Figure 1 This is a diagram showing the cross-sectional shape of an organic transistor.

[0049] Figure 2is a view showing a cross-sectional shape of an organic transistor which is one embodiment of the electronic device of the present application.

[0050] Figure 3 is a graph of a H-NMR chart of the fluorine-based resin 1 manufactured in Example 1. 1 is a graph of a H-NMR chart. DETAILED DESCRIPTION

[0051] Hereinafter, a fluorine-based resin which is one embodiment of the present application will be described in detail.

[0052] The fluorine-based resin of the present application is a fluorine-based resin having a repeating unit represented by the following formula (1), and a repeating unit containing a fluorine atom.

[0053] [Chemical Formula 5]

[0054]

[0055] The above formula (1) in the fluorine-based resin of the present application has a photocrosslinkable group. Due to this, the fluorine-based resin exhibits high photoreactivity, and in a film obtained by coating the resin, it is possible to selectively insolubilize only a portion to which light is irradiated.

[0056] In formula (1), R1represents a hydrogen atom or a methyl group.

[0057] In formula (1), L1represents a single bond or a divalent linking group.

[0058] As the divalent linking group in L1, a divalent linking group formed by combining at least two or more groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-0-), a carbonyl group (-C(=0)-), and an imino group (-NH-) is preferable. Due to this, it is possible to form a film which is flat and free from cracks.

[0059] As the linear alkylene group having 1 to 10 carbon atoms, specifically, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, and the like can be given.

[0060] As the branched alkylene group having 3 to 10 carbon atoms, specifically, for example, dimethylmethylene, methylethylene, 2,2-dimethylpropylene, 2-ethyl-2-methylpropylene, and the like can be given.

[0061] As the cyclic alkylene group having 3 to 10 carbon atoms, specifically, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like can be given, of which cyclohexylene is preferable.

[0062] As the arylene group having 6 to 12 carbon atoms, specifically, for example, a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, a 2,2'-methylenebisphenyl group, and the like can be given, of which a phenylene group is preferred.

[0063] Of these divalent linking groups, an ester bond (-C(=0)0-) or a linking group in which a phenylene group and an ether group are combined is more preferred, and further, (-C(=0)0-) is preferred.

[0064] In formula (1), A represents an m-valent linking group.

[0065] m represents an integer of 3 or more, preferably an integer of 3 to 5, more preferably an integer of 3 to 4, and further preferably 3.

[0066] A can be an m-valent hydrocarbon group having 1 to 24 carbon atoms which can have a substituent, from the viewpoint of improving the solubility of the resulting resin in organic solvents and fluorine-based solvents.

[0067] As the substituent which the m-valent hydrocarbon group A can have, for example, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, and the like can be given.

[0068] As the alkyl group, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms is preferred, more preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group, and the like, and further preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group.

[0069] As the alkoxy group, for example, an alkoxy group having a linear or branched alkyl group having 1 to 16 carbon atoms, for example, a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, an isobutoxy group, a n-pentoxy group, a n-hexyloxy group, an isohexyloxy group, a n-heptyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a n-dodecyloxy group, a n-tetradecyloxy group, a 2-ethylhexyloxy group, a 3-ethylheptyloxy group, a 2-hexyldecyloxy group, and the like, particularly preferably a group selected from the group consisting of a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, an isobutoxy group, a n-pentoxy group, a n-hexyloxy group, an isohexyloxy group, a n-heptyloxy group, and a n-octyloxy group.

[0070] As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be given, of which a fluorine atom and a chlorine atom are preferred.

[0071] Of the m-valent hydrocarbon group A, preferably, one linking group selected from the group consisting of the following formulae (a-1) to (a-4).

[0072] [Chem. 6]

[0073]

[0074] In formulae (a-1) to (a-4), *L indicates a bonding position to L1in the above formula (1), and the preceding * of the carbon atom indicates a bonding position to the oxygen atom constituting the ester group in the above formula (1).

[0075] From the reason of easiness of the reaction in the monomer synthesis, the m-valent hydrocarbon group A is preferably one of the 3-valent linking groups in the group consisting of formula (a-1), formula (a-2), and formula (a-3), more preferably a 3-valent linking group of formula (a-1) or formula (a-2), and further preferably a 3-valent linking group of formula (a-1).

[0076] In formula (1), R2, R3, R4, R5, and R6 are the same or different and represent one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear 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.

[0077] As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be given, of which a fluorine atom or a chlorine atom is preferred.

[0078] As the linear alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferred, and specifically, for example, a methyl group, an ethyl group, a n-propyl group, and the like can be given, of which a methyl group or an ethyl group is preferred.

[0079] As the branched alkyl group having 3 to 20 carbon atoms, an alkyl group having 3 to 6 carbon atoms is preferred, and specifically, for example, an isopropyl group, a t-butyl group, and the like can be given.

[0080] As the cyclic alkyl group having 3 to 20 carbon atoms, an alkyl group having 3 to 6 carbon atoms is preferred, and specifically, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like can be given, of which a cyclohexyl group is preferred.

[0081] As the linear halogenated alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms is preferred, and specifically, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and the like can be given, of which a trifluoromethyl group is preferred.

[0082] As the alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms is preferred, and specifically, for example, a methoxy group, an ethoxy group, a n-butoxy group, a methoxyethoxy group, and the like can be given.

[0083] As the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferable, and specifically, for example, a phenyl group, an α-methylphenyl group, a naphthyl group, and the like can be given, of which a phenyl group is preferable.

[0084] As the aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 12 carbon atoms is preferable, and specifically, for example, a phenoxy group, a 2-naphthoxy group, and the like can be given, of which a phenoxy group is preferable.

[0085] As the amino group, for example, a primary amino group (-NH2); a secondary amino group such as a methylamino group; a tertiary amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a nitrogen-containing heterocyclic compound (for example, a pyrrolidine, a piperidine, a piperazine, and the like) having a nitrogen atom as a bonding site; and the like can be given.

[0086] From the viewpoint of further improving the solubility in a fluorine-based solvent, photocurability, and liquid repellency of the fluorine-based resin, R2, R3, R4, R5, and R6are preferably a hydrogen atom, an alkyl group, a halogen atom, a linear halogenated alkyl group having 1 to 20 carbon atoms, and further preferably a hydrogen atom.

[0087] As the repeating unit represented by formula (1) containing a photocrosslinkable group (hereinafter, sometimes referred to as a repeating unit B), specifically, for example, the following repeating units B-1 to B-26 can be given, of which B-1 to B-16 and the like are preferable, and B-1, B-2, B-13, and B-16 are particularly preferable. Note that in the following formulae, Me represents a methyl group, Et represents an ethyl group, and Pr represents an isopropyl group.

[0088] [Chemical Formula 7]

[0089]

[0090] [Chemical Formula 8]

[0091]

[0092] [Chemical Formula 9]

[0093]

[0094] [Chemical Formula 10]

[0095]

[0096] [Chemical Formula 11]

[0097]

[0098] The fluorine-based resin of the present application has a repeating unit containing a fluorine atom. Due to this, the fluorine-based resin exhibits liquid repellency and also has high solubility in a fluorine-based solvent.

[0099] The repeating unit including a fluorine atom is preferably a repeating unit represented by the following formula (3).

[0100] [Chemical Formula 12]

[0101]

[0102] In formula (3), R9represents a hydrogen atom or a methyl group.

[0103] In formula (3), L2represents a single bond or a divalent linking group.

[0104] As the divalent linking group in L2, a divalent linking group formed by combining at least two or more 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, or 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)-), or an imino group (-NH-) is preferable. Thereby, a film that is flat and free from cracks can be formed.

[0105] As the linear alkylene group having 1 to 10 carbon atoms, specifically, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, and the like can be mentioned.

[0106] As the branched alkylene group having 3 to 10 carbon atoms, specifically, for example, dimethylmethylene, methylethylene, 2,2-dimethylpropylene, 2-ethyl-2-methylpropylene, and the like can be mentioned.

[0107] As the cyclic alkylene group having 3 to 10 carbon atoms, specifically, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like can be mentioned, of which cyclohexylene is preferable.

[0108] As the arylene group having 6 to 12 carbon atoms, specifically, for example, phenylene, xylylene, biphenylene, naphthylene, 2,2'-methylenebisphenylene, and the like can be mentioned, of which phenylene is preferable.

[0109] 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 preferable, and (-C(=O)O-) is further preferable.

[0110] In formula (3), Rf1represents one kind selected from the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.

[0111] The fluorine-based resin of one embodiment of the present application exhibits affinity and liquid repellency to a fluorine-based solvent when Rf1is a fluorinated alkyl group.

[0112] When Rf1is a linear fluorinated alkyl group, as specific examples of Rf1, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or an alkyl group having 10 to 14 carbon atoms substituted with a fluorine atom can be given. In the case where the bonding element of L2to Rf1is oxygen, the substitution position of the fluorine atom in Rf1may be any carbon atom except for the carbon atom directly bonded to oxygen in L2.

[0113] When Rf1is a linear fluorinated alkyl group, Rf1is preferably a group represented by the following formula (4).

[0114] [Chemical Formula 13]

[0115]

[0116] In formula (4), * indicates the bonding position to L2in formula (4).

[0117] In formula (4), X is a hydrogen atom or a fluorine atom.

[0118] In formula (4), y is an integer of 1 to 4, preferably 1 to 2.

[0119] In formula (4), z is an integer of 1 to 14, preferably 2 to 10, further preferably 4 to 8.

[0120] By Rf1being a group represented by formula (4), synthesis of a monomer which is a raw material of the repeating unit represented by formula (3) becomes easier.

[0121] When Rf1is a branched fluorinated alkyl group, as specific examples of Rf1, 1,1,1,3,3,3-hexafluoroisopropyl group, 1-(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, 1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, or 1,1-bis(trifluoromethyl)ethyl group can be given.

[0122] When Rf1is a cyclic fluorinated alkyl group, as specific examples of Rf1, 1,2,2,3,3,4,4,5,5-nonafluorocyclopentyl group, 1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl group can be given.

[0123] The repeating unit represented by the above formula (3) is preferably a repeating unit represented by the following formula (5).

[0124] [Chemical Formula 14]

[0125]

[0126] In formula (5), R10 It represents either a hydrogen atom or a methyl group.

[0127] In equation (5), X is a hydrogen atom or a fluorine atom.

[0128] In equation (5), y is an integer from 1 to 4, preferably from 1 to 2.

[0129] In equation (5), z is an integer from 1 to 14, preferably from 2 to 10, and more preferably from 4 to 8.

[0130] One embodiment of the fluorinated resin of the present invention may contain one repeating unit represented by formula (3) above, or it may contain two or more repeating units. For example, it may contain two repeating units: one having a linear fluoroalkyl group as a repeating unit of Rf1, and the other having a branched fluoroalkyl group as a repeating unit of Rf1. It may also contain two or more repeating units having linear fluoroalkyl groups with different numbers of carbon atoms. One embodiment of the fluorinated resin of the present invention preferably contains one repeating unit represented by formula (3).

[0131] As an example of the present invention, the repeating unit containing fluorine atoms in the fluorine-based resin is specifically one of the group consisting of repeating units represented by the following formulas (C-1) to (C-33).

[0132] [Chemistry 15]

[0133]

[0134] [Chemistry 16]

[0135]

[0136] [Chemistry 17]

[0137]

[0138] As the repeating unit containing fluorine atoms, it is preferably one of the repeating units represented by the above formulas (C-1) to (C-33), more preferably one of the repeating units represented by formulas (C-9) to (C-33), and particularly preferably one of the repeating units represented by formulas (C-14) to (C-21) or one of the repeating units represented by formulas (C-27) to (C-33).

[0139] One aspect of the fluorinated resin of the present invention is preferably a copolymer comprising the repeating unit represented by formula (1) and the repeating unit represented by formula (3) above. That is, one aspect of the fluorinated resin of the present invention is preferably a copolymer represented by formula (6) below.

[0140] [Chemistry 18]

[0141]

[0142] (In formula (6), R1, R9 represent a hydrogen atom or a methyl group, L1, 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 selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, an amino group. m represents an integer of 3 or more, and n represents an integer of m-1. Rf1 represents one selected from the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, and a cyclic fluoroalkyl group having 3 to 15 carbon atoms.)

[0143] 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) described above.

[0144] In formula (6), R9, L2, Rf1 have the same meanings as R9, L2, Rf1 in formula (3) described above.

[0145] The copolymer represented by formula (6) can be a random copolymer or a block copolymer.

[0146] From the viewpoint of improving the solubility in a fluorine-based solvent and making the photocuring more efficient, the fluorine-based resin of one embodiment of the present application preferably contains 10 mol% or more and 90 mol% or less of the repeating unit represented by formula (1) described above, preferably contains 20 mol% or more and 80 mol% or less, and preferably contains 20 mol% or more and 70 mol% or less.

[0147] Further, it is preferable to contain 10 mol% or more and 90 mol% or less of the repeating unit containing a fluorine atom, preferably to contain 20 mol% or more and 80 mol% or less, and preferably to contain 30 mol% or more and 80 mol% or less.

[0148] The fluorine-based resin of one embodiment of the present application preferably further has a repeating unit represented by formula (2).

[0149] [Chemical Formula 19]

[0150]

[0151] In formula (2), R7 represents a hydrogen atom or a methyl group.

[0152] In formula (2), R8represents an alkyl group having 1 to 30 carbon atoms.

[0153] In formula (2), R8represents an alkyl group having 1 to 30 carbon atoms, and 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, eicosyl, heneicosyl, and docosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, isohexyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 2-hexyldecyl, 2-hexylundecyl, 2-octyldodecyl, 2-decyldodecyl, 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, and cycloheptyl, and 3-decylcyclopentyl and 4-decylcyclohexyl. Of these, one selected from the group consisting of linear alkyl groups having 1 to 15 carbon atoms and branched alkyl groups having 3 to 15 carbon atoms is preferable, and a linear alkyl group having 1 to 3 carbon atoms is more preferable, and methyl is particularly preferable.

[0154] As the repeating unit represented by formula (2), specifically, one selected from the group consisting of repeating units 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 is preferable.

[0155] In the fluorine-based resin of one embodiment of the present application, in the case where the repeating unit represented by formula (2) is included, from the viewpoint of improving the solubility in a fluorine-based solvent and making the photocuring more efficient, it is preferable to include 10% by mole or more and 70% by mole or less of the repeating unit represented by formula (1), it is preferable to include 20% by mole or more and 50% by mole or less, and it is preferable to include 30% by mole or more and 50% by mole or less.

[0156] In addition, it is preferable to include 10% by mole or more and 70% by mole or less of the repeating unit represented by formula (2), it is preferable to include 20% by mole or more and 60% by mole or less, and it is preferable to include 30% by mole or more and 50% by mole or less.

[0157] Further, it is preferable to contain 10 mol% or more and 80 mol% or less of the repeating unit containing a fluorine atom, preferably 10 mol% or more and 60 mol% or less, preferably 10 mol% or more and 40 mol% or less, more preferably 10 mol% or more and 30 mol% or less.

[0158] The fluorine-based resin of one embodiment of the present application can contain other monomer repeating units within a range that does not depart from the object of the present application. Examples of the other monomer repeating units include: olefin-based residues such as ethylene residues, propylene residues, and 1-butene residues; vinyl aromatic hydrocarbon-based residues such as styrene residues and α-methylstyrene residues; carboxylic acid vinyl ester-based residues such as vinyl acetate residues, vinyl propionate residues, and vinyl pivalate residues; vinyl ether-based residues such as methyl vinyl ether residues, ethyl vinyl ether residues, and butyl vinyl ether residues; N-substituted maleimide-based residues such as N-methylmaleimide residues, N-cyclohexylmaleimide residues, and N-phenylmaleimide residues; acrylonitrile residues; and methacrylonitrile residues.

[0159] The fluorine-based resin of the present application is not particularly limited in terms of the molecular weight, and for example, a fluorine-based resin with a molecular weight of 2000 to 10,000,000 (g / mol) can be used. From the viewpoint of the solution viscosity and mechanical strength of the obtained resin, the molecular weight is preferably 10,000 to 1,000,000 (g / mol).

[0160] The method for synthesizing the fluorine-based resin of the present application is not particularly limited, and for example, the fluorine-based resin can be synthesized by mixing a monomer that forms the above-described repeating unit B, a monomer that forms the above-described repeating unit containing a fluorine atom, and a monomer that forms an arbitrary other repeating unit, and performing polymerization in an organic solvent using a radical polymerization initiator.

[0161] In the fluorine-based resin of one embodiment of the present application, in the case where the repeating unit represented by Formula (2) is included, the method for synthesizing the fluorine-based resin is not particularly limited, and for example, the fluorine-based resin can be synthesized by mixing a monomer that forms the above-described repeating unit B, a monomer that forms the above-described repeating unit represented by Formula (2), a monomer that forms the above-described repeating unit containing a fluorine atom, and a monomer that forms an arbitrary other repeating unit, and performing polymerization in an organic solvent using a radical polymerization initiator.

[0162] A composition of one embodiment of the present application is described below.

[0163] The composition of one embodiment of the present application contains at least one of an organic solvent and a fluorine-based solvent, and a fluorine-based resin.

[0164] The fluorine-based solvent can dissolve the fluorine-based resin of the present application. By using a fluorine-based solvent as a solvent for dissolving a fluorine-based resin, when an electronic device is produced using a full printing method, damage to a device component in which an organic substance is a main component can be minimized, and the performance of the electronic device can be fully exhibited.

[0165] In the fluorine-based compound constituting the fluorine-based solvent, the content of fluorine atoms is 50% by mass or more and 70% by mass or less, and more preferably 55% by mass or more and 70% by mass or less, relative to the total mass of the fluorine-based compound. If it exceeds 70% by mass, the fluorine-based resin cannot be sufficiently dissolved. In addition, if it is less than 50% by mass, the surface of the organic semiconductor film can be dissolved or swelled when the organic semiconductor film is coated or printed.

[0166] As the fluorine-based solvent included in the composition of the present application, a fluorine-containing hydrocarbon, a fluorine-containing ether, or a fluorine-containing alcohol shown below can be preferably used, and a fluorine-containing hydrocarbon or a fluorine-containing ether can be more preferably used.

[0167] A fluorine-containing hydrocarbon has a low ozone destruction coefficient, and is preferable as the fluorine-based solvent included in the composition of the present application. In particular, a fluorine-containing hydrocarbon in which at least one hydrogen atom of a linear, branched, or cyclic hydrocarbon having 4 to 8 carbon atoms is substituted with a fluorine atom is easy to coat, and is therefore preferable.

[0168] As such a fluorine-containing hydrocarbon, specifically, a fluorine-containing hydrocarbon in which at least one hydrogen atom of butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, or benzene is substituted with a fluorine atom can be exemplified. If it is specifically exemplified, a fluorine-containing hydrocarbon 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, hexafluorobenzene can be exemplified.

[0169] The boiling point of the fluorine-containing hydrocarbon is preferably 200°C or lower, and further preferably 180°C or lower. If the boiling point of the fluorine-containing hydrocarbon is 200°C or lower, the fluorine-containing hydrocarbon is easily removed by evaporation by heating.

[0170] Among the above-described fluorine-containing hydrocarbons, as examples having particularly preferable boiling points, the following can be exemplified.

[0171] 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, hexafluorobenzene can be exemplified.

[0172] In addition, from the viewpoint of a low ozone-depletion coefficient, a fluorine-containing ether can be used as the fluorine-based solvent. The boiling point of the fluorine-containing ether is preferably 200°C or lower, and more preferably 180°C or lower. If the boiling point of the fluorine-containing ether is 200°C or lower, the fluorine-containing ether is easily removed from the fluorine-based resin film by heating.

[0173] As examples of the preferred fluorine-containing ether, 1,1,2,3,3,3-hexafluoro-l-(2,2,2-trifluoroethoxy)propane, 1,1,2,3,3,3-hexafluoro-l-(2,2,3,3,3-pentafluoropropoxy)propane, 1,1,2,3,3,3-hexafluoro-l-(2,2,3,3-tetrafluoropropoxy)propane, 2,2,3,3,3-pentafluoro-l-(l,l,2,2-tetrafluoroethoxy)propane, 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane, methyl perfluorobutyl ether, or ethyl nonafluorobutyl ether can be exemplified.

[0174] As the fluorine-containing ether having a preferred boiling point, 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, methoxy perfluoroheptene, and the like can be exemplified.

[0175] As the fluorine-based solvent, a fluorine-containing alcohol can be used. The boiling point of the fluorine-containing alcohol used is preferably 200°C or lower, and more preferably 180°C or lower. If the boiling point of the fluorine-containing alcohol is 200°C or lower, the fluorine-containing alcohol is easily removed by heating.

[0176] As examples of the preferred fluorine-containing alcohol, 1H, 1H-trifluoroethanol, 1H, 1H-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, 1H, 1H, 3H-hexafluorobutanol can be exemplified.

[0177] Further, in order to further improve the solubility of the fluorine-based resin, two or more kinds of fluorine-based solvents can also be contained.

[0178] As the organic solvent used in the composition of the present application, an organic solvent other than the fluorine-based solvent is meant. As the organic solvent, there is no particular limitation as long as the fluorine-based resin of the present application is soluble therein, and examples include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, cumene, amylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butanediol, ethylene glycol, benzyl alcohol, glycerol, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradeca-hydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetylene 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, phenyl ethyl ketone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, limonene, and the like. In order to obtain a film having preferable properties, an organic solvent having a high solvency for dissolving the fluorine-based resin is suitably used, and xylene, propylene glycol monomethyl ether acetate are preferable. Alternatively, a mixed solvent obtained by mixing two or more of the above-described solvents in an appropriate ratio can be used.

[0179] The composition of one embodiment of the present application in which the fluorine-based resin is combined with a solvent selected from at least one of an organic solvent and a fluorine-based solvent preferably contains 1 wt% or more and 50 wt% or less of the fluorine-based resin, and contains 50 wt% or more and 99 wt% or less of the solvent.

[0180] Further, the composition of one embodiment of the present application can contain a photosensitizer. The photosensitizer only needs to promote the cross-linking reaction of the photo-crosslinkable group.

[0181] As the photosensitizer, for example, the following can be given: benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, cyclohexanone, and the like; carbonyl compounds; diketones such as benzil and the like; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, tetramethylthiuram disulfide, and the like; acetophenones such as acetophenone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methoxybenzophenone, 2,4,6-trimethoxybenzophenone, and the like; sulfonyl halides such as p-toluenesulfonyl chloride, I-naphthalenesulfonyl chloride, 1,3-benzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, p-acetamidobenzenesulfonyl chloride, and the like; aromatic nitro compounds such as 5-nitrofluorene, 5-nitroacenaphthene, N-acetyl-4-nitro-1-naphthylamine, beclamide, and the like; coumarins such as 7-diethylamino-3-thiacylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), and the like; halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, 1,1,2,2-tetrabromoethane, and the like; nitrogen derivatives such as diazomethane, azobis(isobutyronitrile), hydrazine, trimethylbenzylammonium chloride, and the like; pigments such as ethionine, thionine, methylene blue, and the like. By adding the photosensitizer, the fluorine-based resin of one embodiment of the present application can be crosslinked (insolubilized) with a lower exposure amount. In addition, the sensitizer can be used in combination with two or more as needed.

[0182] The composition of one embodiment of the present application, the photosensitizer, and at least one solvent selected from an organic solvent and a fluorine-based solvent preferably contains the fluorine-based resin at 1 wt% or more and 50 wt% or less, contains the solvent at 50 wt% or more and 99 wt% or less, and contains the photosensitizer at 0.001 wt% or more and 5 wt% or less.

[0183] A pattern of one embodiment of the present application is described below.

[0184] A pattern can be formed using the fluorine-based resin of the present application. In more detail, a photocrosslinked product is obtained using the fluorine-based resin of the present application or a composition thereof, and a pattern is formed.

[0185] First, a coating film of the fluorine-based resin is formed on the surface of a substrate by a publicly known coating film formation method. As the substrate, for example, various glass plates; polyester such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; thermoplastic plastic sheets of polycarbonate, polymethyl methacrylate, polysulfone, and polyimide; epoxy resins; polyester resins; thermosetting plastic sheets such as poly(meth)acrylic resins, and the like can be given.

[0186] As a method for forming the coating film, for example, spin coating, drop coating, dip coating, doctor-blade coating, pad printing, squeegee coating, roll coating, 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, adhesion contrast printing, and the like can be used.

[0187] Next, the coating film is dried. By drying, the solvent is volatilized, and a coating film having no tackiness is obtained. The drying conditions vary depending on the boiling point of the solvent used and the blending ratio, and the like, and it is preferable that a wide range of 50 to 150°C for 10 to 2000 seconds or so can be used.

[0188] At the time of coating film formation, when a coating film having a prescribed shape, i.e., the same shape as the target pattern, is formed using a printing method, by performing exposure, the coating film having the prescribed shape is photo-crosslinked, a photo-crosslinked product is obtained and is immobilized, and a pattern can be formed.

[0189] On the other hand, in the case where a coating film having a prescribed shape is not formed at the time of coating film formation, a pattern can be formed from the coating film using a photolithography technique. In the case where a photolithography technique is used, first, a mask having a prescribed shape, i.e., a shape that can form a target pattern, is interposed, and the dried coating film is exposed to light, and is photo-crosslinked.

[0190] At the time of curing the fluorine-based resin of the present application by photo-crosslinking, a radioactive ray such as ultraviolet rays, visible light, and the like can be used, and for example, ultraviolet rays having a wavelength of 245 to 435 nm can be exemplified. The irradiation amount is appropriately changed depending on the composition of the resin, and for example, 10 to 5000 mJ / cm 2 From the viewpoint of preventing a decrease in the degree of crosslinking and improving the economy by shortening the process time, the irradiation amount is preferably 100 to 4000 mJ / cm 2 As a specific light irradiation device or light source, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium- or high-pressure mercury lamps, super-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and the like can be exemplified.

[0191] The irradiation of ultraviolet rays is usually performed in the atmosphere, but can also be performed in an inert gas or under a flow of a certain amount of inert gas, as needed. The above-mentioned photosensitizer can also be added as needed to promote the photocrosslinking reaction. Then, development is performed using a developer to remove the unexposed portions. As the developer, any solvent that dissolves the unhardened fluorine-based resin can be used, such as an aromatic solvent such as benzene, toluene, xylene, or the like; an ether-based solvent such as dioxane, diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, or the like; a ketone-based solvent such as acetone, methyl ethyl ketone, or the like; an ester-based solvent such as ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether acetate, or the like; a fluorine-based solvent such as 2H, 3H-decafluoropentane, 1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane, 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, hexafluorobenzene, 2, 2, 3, 3-tetrafluoro-l-propanol, 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-l-pentanol, 1H, 1H, 7H-dodecafluoro-l-heptanol, 2, 2, 3, 3, 4, 4, 4-heptafluoro-l-butanol, or the like.

[0192] The development time is preferably 30 to 300 seconds. In addition, the development method can be any of a puddle method, a dip method, or the like. After development, the substrate is cleaned using a solvent and air-dried using compressed air or compressed nitrogen gas, whereby the solvent on the substrate is removed. Subsequently, a heating treatment is performed using a hot plate, an oven, or the like, preferably at 40 to 150°C for 5 to 90 minutes, whereby the pattern is formed.

[0193] The substrate surface within the pixels can also be cleaned after the pixel pattern is formed by the above-mentioned photolithography process. For example, the substrate surface can be cleaned by irradiation of short-wavelength ultraviolet rays such as a low-pressure mercury lamp or an excimer UV, or by a photoablation process. The photoablation process refers to a process in which short-wavelength ultraviolet rays are irradiated in the presence of ozone gas. The short-wavelength ultraviolet rays refer to light having a main peak at a wavelength of 100 to 300 nm.

[0194] Thus, the fluorine-based resin of the present application is itself soluble in a fluorine-based solvent or an organic solvent, and is insolubilized in the solvent used by crosslinking the photocrosslinkable groups possessed by the side chains through light irradiation. By utilizing this property, the fluorine-based resin of the present application can be used as a negative resist in which the portions to which light is not irradiated are removed by a fluorine-based solvent or an organic solvent when the fluorine-based resin is crosslinked by light irradiation.

[0195] After the fluorine-based resin of the present application is patterned, the contact angle of the portion in which the fluorine-based resin is crosslinked (the portion outside the pattern) with respect to the ink used to form the functional layer is preferably 40° or greater, and more preferably 50° or greater, in order to avoid the spreading of the wetting of the ink.

[0196] The fluorine-based resin of the present application can be formed into a protective film using the same method as the pattern, such as a coating film formation method, photocrosslinking, development, or the like.

[0197] The fluorine-based resin of the present application has excellent liquid repellency and can be used in a pattern material in the production of an organic transistor element, a color filter, or an organic EL element. In addition, the fluorine-based resin of the present application can be used in an electronic device including the organic transistor element, the color filter, or the organic EL element.

[0198] Hereinafter, an electronic device according to one embodiment of the present application will be described in detail.

[0199] The fluorine-based resin of the present application can be used in an electronic device, and more specifically, an electronic device having a photo-crosslinked product of a composition including the fluorine-based resin of the present application and a solvent selected from at least one of an organic solvent and a fluorine-based solvent. As the electronic device, an organic transistor can be exemplified.

[0200] A general organic transistor is obtained by having a gate insulating layer on a substrate, further forming an organic semiconductor layer on the gate insulating layer, and attaching a source, a drain, and a gate. An example of the element structure of the organic transistor is shown as a cross-sectional view in Figure 1 . 1001 is a bottom-gate-top-contact type element structure, 1002 is a bottom-gate-bottom-contact type element structure, 1003 is a top-gate-top-contact type element structure, and 1004 is a top-gate-bottom-contact type element structure. 1 represents an organic semiconductor layer, 2 represents a substrate, 3 represents a gate, 4 represents a gate insulating layer, 5 represents a source, and 6 represents a drain.

[0201] Figure 2 An example of the organic transistor according to the present application is shown. Figure 2 The organic transistor 1005 shown corresponds to the bottom-gate-bottom-contact type in Figure 1 . 7 represents a pattern, and 8 represents a protective film layer.

[0202] In the organic transistor, the substrate that can be used is not particularly limited as long as it can ensure sufficient planarity for producing an element, and for example, inorganic material substrates such as glass, quartz, alumina, highly doped silicon, silicon oxide, tantalum oxide, tantalum pentoxide, indium tin oxide, and the like; plastics; metals such as gold, copper, chromium, titanium, aluminum, and the like; ceramics; coated paper; surface-coated nonwoven fabric, and the like can be exemplified, and a composite material including these materials or a material in which these materials are layered can also be used. In addition, in order to adjust the surface tension, the surfaces of these materials can also be coated.

[0203] As the plastic used as the substrate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethyl pentene-1, polypropylene, cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinyl phenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyether sulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, styrene block copolymer, and the like can be exemplified. In addition, two or more of the above plastics can be used in a stacked manner as the substrate.

[0204] The organic semiconductor that can be used in the organic semiconductor layer is not particularly limited, and both N-type and P-type organic semiconductors can be used, and a bipolar transistor that combines N-type and P-type can also be used. In addition, both low-molecular and high-molecular organic semiconductors can be used, and they can also be used in a mixed manner. As specific compounds of the organic semiconductor, for example, compounds represented by the following Formulas (D-1) to (D-11) and the like can be exemplified.

[0205] [Chemical Formula 20]

[0206]

[0207] [Chemical Formula 21]

[0208]

[0209] [Chemical Formula 22]

[0210]

[0211] [Chemical Formula 23]

[0212]

[0213] In this invention, methods for forming an organic semiconductor layer include vacuum evaporation of the organic semiconductor, coating or printing by dissolving the organic semiconductor in an organic solvent, etc. However, there are no limitations as long as the method can form a thin film of the organic semiconductor layer. The concentration of the solution used for coating or printing with a solution formed by dissolving the organic semiconductor layer in an organic solvent varies depending on the structure of the organic semiconductor and the solvent used. From the viewpoint of forming a more uniform semiconductor layer and reducing the layer thickness, a concentration of 0.5% to 5 wt% is preferred. As for the organic solvent, there are no limitations as long as it is dissolved at a certain concentration sufficient for film formation of the organic semiconductor. Examples include: hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decahydronaphthalene, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a mixture of dimethylnaphthalene isomers, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetrahydronaphthalene, octylbenzene, cyclohexylbenzene, 1,2-dimethylnaphthalene, etc. Chlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butanediol, ethylene glycol, benzyl alcohol, glycerol, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, di... Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradehydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetylene decahydro-2-naphthol, dipropylene glycol dimethyl ether 2,6-Dimethyl anisole, 1,2-Dimethyl anisole, 2,3-Dimethyl anisole, 3,4-Dimethyl anisole, 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, limonene, etc. To obtain a crystalline film with preferred properties, solvents with high solubility for dissolving organic semiconductors and boiling points of 100°C or higher are suitable, preferably xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, and decahydro-2-naphthol. Alternatively, mixed solvents formed by mixing two or more of the above solvents in appropriate proportions can also be used.

[0214] In the organic semiconductor layer, various organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added as needed in the form of a solid or a dispersion liquid in which the nanoparticles are dispersed in water or an organic solvent, and a protective film can be formed by applying a polymer solution on the above-mentioned insulating layer. Furthermore, various moisture-proof coating, light resistance coating, and the like can be performed on the protective film as needed.

[0215] As the conductive material that can be used in the present application for the gate, source, or drain, conductive materials such as 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, carbon nanotube, or doped conductive polymers such as PEDOT-PSS, or the like, can be exemplified, and these conductive materials can be used in multiple or stacked. In addition, in order to improve the injection efficiency of carriers, surface treatment can be performed on these electrodes using a surface treatment agent. As such a surface treatment agent, benzene thiol, pentafluorobenzene thiol, or the like can be exemplified.

[0216] In addition, the method of forming the electrode on the above-mentioned substrate, insulating layer, or organic semiconductor layer is not particularly limited, and methods such as evaporation, high-frequency sputtering, electron beam sputtering, or the like can be exemplified, and methods such as solution spin coating, drop coating, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, super-flexographic printing, screen printing, inkjet printing, letterpress reverse printing, or the like can be performed using an ink obtained by dissolving nanoparticles of the above-mentioned conductive material in water or an organic solvent.

[0217] The fluorine-based resin of the present application can be suitably used for a pattern, a protective film layer in an organic transistor.

[0218] From the viewpoint of the practicality of the organic transistor element, the mobility of the organic transistor of one embodiment of the present application is preferably 0.20 cm 2 or more.

[0219] From the viewpoint of the practicality of the organic transistor element, the on current / off current ratio of the organic transistor of one embodiment of the present application is preferably 10 5 or more.

[0220] From the viewpoint of the practicality of the organic transistor element, the organic transistor of one embodiment of the present application preferably has no hysteresis of the current between the source and the drain.

[0221] Example

[0222] The present application is further described in detail by way of examples below, but the present application is not limited to these examples.

[0223] In the examples, the following conditions and devices were used.

[0224] <Monomer purity>

[0225] Gas chromatograph: GC 2014 (trade name) manufactured by Shimadzu Corporation

[0226] Column: Rxi-1HT (trade name) manufactured by RESTEK Corporation, 30 m

[0227] The purity of the monomer was analyzed using the above gas chromatograph (GC).

[0228] <Composition of fluorine-based resin>

[0229] The composition was determined by proton nuclear magnetic resonance spectroscopy (H-NMR) using a nuclear magnetic resonance measuring device (JNM-ECZ 400S (trade name) manufactured by JEOL Ltd.). 1

[0230] <Spin coating>

[0231] An MS-A100 manufactured by Mikasa Corporation was used.

[0232] <Measurement of film thickness>

[0233] The measurement was performed using a Dektak XT Stylus Profiler manufactured by Bruker Corporation.

[0234] <UV irradiation>

[0235] A UV mask lithography machine, UPE-1605MA (trade name) manufactured by Ushio Lighting Co., Ltd., was used to adjust the UV irradiation time by changing the conveyance speed under the conditions of a UV intensity of 14.2 mW / cm 2

[0236] <Inkjet printing>

[0237] A solution of an organic semiconductor (di-n-hexyl dithienobenzodithiophene) synthesized according to the production method of Japanese Patent Application Publication No. 2015-224238 was filled into a cartridge having a basic droplet amount of 10 pL, and printing was performed using an inkjet device (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Corporation, stage temperature 30°C, cartridge temperature 30°C).

[0238] <Laser microscope>

[0239] An inkjet-printed organic semiconductor layer or pattern was confirmed using a laser microscope, OPTELICS HYBRID (trade name) manufactured by Lasertec Corporation.

[0240] In the examples, the following results were obtained.

[0241] ​​Synthesis Example 1 (Synthesis of photocrosslinkable monomer 1)

[0242] Under a nitrogen atmosphere, a 200 mL flask was charged with glyceryl monomethacrylate (BLEMMER GLM, Nippon Oil) 6 g, triethylamine 8.6 g, and tetrahydrofuran 18 g, and mixed well. Separately, a glass bottle was charged with cinnamoyl chloride 14.1 g and tetrahydrofuran 42 g under a nitrogen atmosphere and dissolved. Then, nitrogen was made to flow into the flask charged with glyceryl monomethacrylate, triethylamine, and tetrahydrofuran, and the solution in which cinnamoyl chloride was dissolved was added dropwise using a dropping funnel, and stirred for 22 hours. Then, the salt as a byproduct was removed by filtration, and tetrahydrofuran was removed using an aspirator. Then, the product was dissolved in 50 g of toluene, washed with an aqueous sodium bicarbonate solution three times, and vacuum-dried. The resulting substance after drying was identified as a substance represented by the following formula (7) (photocrosslinkable monomer 1) by H-NMR and gas chromatography analysis. 1 The results of H-NMR and gas chromatography analysis confirmed that it was a substance represented by the following formula (7) (photocrosslinkable monomer 1).

[0243] (Photocrosslinkable monomer 1)

[0244] [Chemical Formula 24]

[0245]

[0246] Example 1 (Polymerization of fluorine-based resin 1)

[0247] A 75 mL glass ampoule was charged with 6.78 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1H, 1H, 2H, 2H-perfluoro-n-octyl methacrylate 9.10 g, PERHEXYL ND (manufactured by Nippon Oil) 0.27 g as a polymerization initiator, and 2-butanone 37 g, and after repeating nitrogen replacement and pressure release, the ampoule was sealed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and held for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise into methanol 500 mL to precipitate it, and then washed twice with methanol 300 mL. Further, vacuum drying was performed at 30°C for 8 hours, whereby 13.8 g of fluorine-based resin 1 (yield: about 87%) was obtained. The composition of the fluorine-based resin 1 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-perfluoro-n-octyl methacrylate (fluorine-based unit) [C-29] = 38 / 62 (mole %), and it was a copolymer represented by the following formula (8). 1 The results of H-NMR measurement are shown in 1 . Figure 3 .

[0248] (Fluorine-based resin 1)

[0249] [Chemical Formula 25]

[0250]

[0251] Synthesis Example 2 (Synthesis of Photocrosslinkable Monomer 2)

[0252] 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 mixture was stirred at 40 °C for 4 hours while being dried under vacuum to obtain 4-chlorocinnamoyl chloride. Then, under a nitrogen atmosphere, 1.7 g of glyceryl monomethacrylate (BLEMMER GLM, Nippon Oil), 3 g of triethylamine, and 5.1 g of toluene were added to a 100 mL flask and mixed thoroughly. Separately, under a nitrogen atmosphere, 5.3 g of 4-chlorocinnamoyl chloride and 16 g of toluene were added to a glass bottle and dissolved. Nitrogen gas was then introduced into the flask containing glyceryl monomethacrylate, triethylamine, and toluene, and a solution of pCl-cinnamoyl chloride was added dropwise using a dropping funnel, while stirring for 22 hours. The salts, which were byproducts, were then removed by filtration. The mixture was then washed three times with an aqueous sodium bicarbonate solution and dried under vacuum. The resulting substance... 1 The results of H-NMR and gas chromatography analysis confirmed that it was the compound represented by the following formula (9) (photocrosslinking monomer 2).

[0253] (GC purity 93%)

[0254] (Photocrosslinking monomer 2)

[0255] [Chemistry 26]

[0256]

[0257] Example 2 (Polymerization of Fluoropolymer 2)

[0258] 2.31 g of the photocrosslinking monomer 2 obtained in Synthesis Example 2, 2.85 g of 1H,1H,2H,2H-tridecylfluoro-n-octyl methacrylate, 0.09 g of PERHEXYL ND (Nippon Oil Manufacturing Co., Ltd.) as a polymerization initiator, and 12 g of 2-butanone were added to a 75 mL glass ampoule. After repeated nitrogen replacement and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a constant temperature bath at 45 °C for 24 hours to carry out free radical polymerization. After the polymerization reaction was completed, the polymer solution was removed from the ampoule and added dropwise to 200 mL of methanol to precipitate the polymer solution. The solution was then washed twice with 100 mL of methanol. The solution was then dried under vacuum at 30 °C for 8 hours to obtain 3.0 g of fluorinated resin 2 (yield: approximately 61%). The fluorinated resin 2 was then... 1H-NMR measurement confirmed that the composition was the copolymer represented by the following formula (10) of the photocrosslinkable monomer 2 (photocrosslinkable group unit 2) [B-13] / 1H, 1H, 2H, 2H- tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 36 / 64 (mole %).

[0259] (Fuorine-based resin 2)

[0260] [Chemical 27]

[0261]

[0262] Synthesis Example 3 (Synthesis of photocrosslinkable monomer 3)

[0263] Using (E)-3-(4-methylphenyl)-2-propenoic acid instead of 4-chlorocinnamic acid, and otherwise, the synthesis was performed in the same manner as in Synthesis Example 2. As a result of analysis, it was confirmed that the obtained substance was a compound represented by the following formula (11) (photocrosslinkable monomer 3). (GC purity 89%)

[0264] (Photocrosslinkable monomer 3)

[0265] [Chemical 28]

[0266]

[0267] Example 3 (Polymerization of fluorine-based resin 3)

[0268] In a glass ampoule having a capacity of 75 mL, 2.30 g of the photocrosslinkable monomer 3 obtained in Synthesis Example 3, 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate 2.95 g, PERHEXYL ND (manufactured by Nippon Oil and Fats Co., Ltd.) 0.09 g as a polymerization initiator, and 2-butanone 12 g were added, nitrogen substitution and pressure release were repeated, and then, the ampoule was sealed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out from the ampoule, and the polymer solution was added dropwise into methanol 200 mL to precipitate, and then, the precipitate was washed twice with methanol 100 mL. Further, the precipitate was vacuum-dried at 30°C for 8 hours, whereby 4.2 g of the fluorine-based resin 3 (yield: about 84%) was obtained. The composition of the fluorine-based resin 3 was confirmed by H-NMR measurement. 1 H-NMR measurement confirmed that the composition was the copolymer represented by the following formula (12) of the photocrosslinkable monomer 3 (photocrosslinkable group unit 3) [B-2] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 37 / 63 (mole %).

[0269] (Fuorine-based resin 3)

[0270] [Chemical 29]

[0271]

[0272] Synthesis Example 4 (Synthesis of photocrosslinkable monomer 4)

[0273] Using 3-(trifluoromethyl)cinnamic acid instead of 4-chlorocinnamic acid, synthesis was performed in the same manner as in Synthesis Example 2. As a result of analysis, it was confirmed that the obtained substance was a compound represented by the following formula (13) (photocrosslinkable monomer 4) (GC purity 81%).

[0274] (Photocrosslinkable monomer 4)

[0275] [Chemical Formula 30]

[0276]

[0277] Example 4 (Polymerization of fluorine-based resin 4)

[0278] In a glass ampoule having a capacity of 75 mL, 2.78 g of the photocrosslinkable monomer 4 obtained in Synthesis Example 4, 1H, 1H, 2H, 2H- tridecafluoro-n-octyl methacrylate 2.69 g, PERHEXYL ND (manufactured by Nippon Oil and Fats Co., Ltd.) 0.08 g as a polymerization initiator, and 2-butanone 13 g were added, and after repeating nitrogen substitution and pressure release, fusion sealing was performed under a reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was left for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out from the ampoule, and was dropped into methanol 200 mL to precipitate, and was washed twice with methanol 100 mL. Further, vacuum drying was performed at 30°C for 8 hours, whereby 4.1 g of the fluorine-based resin 4 (yield: about 82%) was obtained. The composition of the fluorine-based resin 4 was confirmed by H-NMR measurement to be photocrosslinkable monomer 4 (photocrosslinkable monomer unit 4) [B-16] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 37 / 63 (molar %), and it was a copolymer represented by the formula (14). 1 H-NMR measurement, and it was confirmed that the composition was photocrosslinkable monomer 4 (photocrosslinkable monomer unit 4) [B-16] / 1H, 1H, 2H, 2H- tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 37 / 63 (molar %), and it was a copolymer represented by the formula (14).

[0279] (Fluorine-based resin 4)

[0280] [Chemical Formula 30]

[0281]

[0282] Example 5 (Polymerization of fluorine-based resin 5)

[0283] In a glass ampoule of 75 mL in capacity, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 25 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then fusion sealing was performed under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and was dropped into 500 mL of methanol to precipitate, and then was washed twice with 300 mL of methanol. Further, vacuum drying was performed at 30°C for 8 hours, whereby 8.4 g of the fluorine-based resin 5 (yield: about 83%) was obtained. The composition of the fluorine-based resin 5 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (fluorine-based unit 2) [C-27] = 39 / 61 (mole %), which was a copolymer represented by Formula (15). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (fluorine-based unit 2) [C-27] = 39 / 61 (mole %), which was a copolymer represented by Formula (15).

[0284] (Fluorine-based resin 5)

[0285] [Chemical Formula 32]

[0286]

[0287] Example 6 (Polymerization of Fluorine-based Resin 6)

[0288] In a glass ampoule of 75 mL in capacity, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 25 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then fusion sealing was performed under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and was dropped into 500 mL of methanol to precipitate, and then was washed twice with 300 mL of methanol. Further, vacuum drying was performed at 30°C for 8 hours, whereby 7.0 g of the fluorine-based resin 6 (yield: about 69%) was obtained. The composition of the fluorine-based resin 6 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 2, 2, 3, 3, 3-pentafluoropropyl methacrylate (fluorine-based unit 3) [C-25] = 39 / 61 (mole %), which was a copolymer represented by Formula (16). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (fluorine-based unit 2) [C-27] = 39 / 61 (mole %), which was a copolymer represented by Formula (15).

[0289] (Fluorine-based resin 6)

[0290] [Chemical Formula 33]

[0291]

[0292] Example 7 (polymerization of fluorine-based resin 7)

[0293] In a glass ampoule having a capacity of 75 mL, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 25 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then the ampoule was sealed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept therein for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise into 500 mL of methanol to precipitate the polymer. The precipitated polymer was washed twice with 300 mL of methanol. Further, the polymer was vacuum-dried at 30°C for 8 hours, whereby 4.3 g of the fluorine-based resin 7 (yield: about 43%) was obtained. The composition of the fluorine-based resin 7 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 5H-octafluoropentyl methacrylate (fluorine-based unit 4) [C-23] = 40 / 60 (mole %), which was a copolymer represented by Formula (17). 1 H-NMR measurement, and was confirmed to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 5H-octafluoropentyl methacrylate (fluorine-based unit 4) [C-23] = 40 / 60 (mole %), which was a copolymer represented by Formula (17).

[0294] (Fluorine-based resin 7)

[0295] [Chem. 34]

[0296]

[0297] Example 8 (polymerization of fluorine-based resin 8)

[0298] In a glass ampoule having a capacity of 75 mL, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 25 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then the ampoule was sealed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept therein for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise into 500 mL of methanol to precipitate the polymer. The precipitated polymer was washed twice with 300 mL of methanol. Further, the polymer was vacuum-dried at 30°C for 8 hours, whereby 0.8 g of the fluorine-based resin 8 (yield: about 8%) was obtained. The composition of the fluorine-based resin 8 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable 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] = 40 / 60 (mole %), which was a copolymer represented by Formula (17). 1H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / methyl methacrylate 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl ester (fluorine-based unit 5) [C-24] = 41 / 59 (mole %), and was a copolymer represented by Formula (18).

[0299] (Fuorine-based resin 8)

[0300] [Chemical 35]

[0301]

[0302] Example 9 (polymerization of fluorine-based resin 9)

[0303] In a glass ampoule having a capacity of 75 mL, 8.2 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 3.1 g of methyl methacrylate 1H, 1H, 2H, 2H-tridecafluoro-n-octyl ester, 0.18 g of PERHEXYL ND (manufactured by Nippon Oil and Fats Co., Ltd.) as a polymerization initiator, and 26 g of 2-butanone were added, nitrogen replacement and pressure reduction were repeated, and then the ampoule was sealed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise into methanol 500 mL to precipitate the polymer, and then the polymer was washed twice with methanol 300 mL. Further, the polymer was vacuum-dried at 30°C for 8 hours, whereby 8.8 g of the fluorine-based resin 9 (yield: about 88%) was obtained. The composition of the fluorine-based resin 9 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / methyl methacrylate 1H, 1H, 2H, 2H-tridecafluoro-n-octyl ester (fluorine-based unit 1) [C-29] = 26 / 74 (mole %), and was a copolymer represented by Formula (19). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / methyl methacrylate 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl ester (fluorine-based unit 5) [C-24] = 41 / 59 (mole %), and was a copolymer represented by Formula (18).

[0304] (Fuorine-based resin 9)

[0305] [Chemical 35]

[0306]

[0307] Example 10 (polymerization of fluorine-based resin 10)

[0308] In a glass ampoule of 75 mL in capacity, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 27 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then fusion sealing was performed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and was dropped into 500 mL of methanol to precipitate the polymer. The polymer was washed twice with 300 mL of methanol. Further, vacuum drying was performed at 30°C for 8 hours, whereby 8.2 g of the fluorine-based resin 10 (yield: about 82%) was obtained. The composition of the fluorine-based resin 10 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 15 / 85 (mole %), which was a copolymer represented by the formula (20). 1 H-NMR measurement, the composition was confirmed to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 15 / 85 (mole %), which was a copolymer represented by the formula (20).

[0309] (Fluorine-based resin 10)

[0310] [Chemical Formula 37]

[0311]

[0312] Example 11 (Production of fluorine-based resin 11)

[0313] In a glass ampoule of 15 mL in capacity, 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 (manufactured by Nippon Oil & Fats Corporation) as a polymerization initiator, and 3.1 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then fusion sealing was performed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was kept for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and was dropped into 100 mL of methanol to precipitate the polymer. The polymer was washed twice with 100 mL of methanol. Further, vacuum drying was performed at 30°C for 8 hours, whereby 1.1 g of the fluorine-based resin 11 (yield: about 83%) was obtained. The composition of the fluorine-based resin 11 was confirmed by H-NMR measurement to be photocrosslinkable monomer 1 (photocrosslinkable 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 (mole %), which was a copolymer represented by the formula (21). 1 H-NMR measurement, the composition was confirmed to be photocrosslinkable monomer 1 (photocrosslinkable group unit 1) [B-1] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-29] = 15 / 85 (mole %), which was a copolymer represented by the formula (20).

[0314] (Fluorine-based resin 11)

[0315] [Chem. 38]

[0316]

[0317] Synthesis Example 5 (Synthesis of photocrosslinkable monomer 5)

[0318] Using 4-(trifluoromethyl)cinnamic acid instead of 4-chlorocinnamic acid, synthesis was performed in the same manner as in Synthesis Example 2. As a result of analysis, it was confirmed that the obtained substance was a compound represented by the following formula (22) (photocrosslinkable monomer 5) (GC purity 83%).

[0319] (Photocrosslinkable monomer 5)

[0320] [Chem. 39]

[0321]

[0322] Example 12 (Polymerization of fluorine-based resin 12)

[0323] In a glass ampoule having a capacity of 75 mL, 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 (a product of Nippon Oil & Fats Co., Ltd.) as a polymerization initiator, and 13 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then fusion sealing was performed under reduced pressure. The ampoule was placed in a constant-temperature bath at 45°C, and was left to stand for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and was added dropwise to methanol 200 mL to precipitate the polymer, and then the polymer was washed twice with methanol 100 mL. Further, vacuum drying was performed at 30°C for 8 hours, whereby 4.1 g of the fluorine-based resin 12 (yield: about 83%) was obtained. The composition of the fluorine-based resin 12 was confirmed by H-NMR measurement to be photocrosslinkable monomer 5 (photocrosslinkable monomer unit 5) [B-15] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 36 / 64 (mole %), and to be a copolymer represented by the following formula (23). 1 H-NMR measurement, and to be photocrosslinkable monomer 5 (photocrosslinkable monomer unit 5) [B-15] / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [B-29] = 36 / 64 (mole %), and to be a copolymer represented by the following formula (23).

[0324] (Fluorine-based resin 12)

[0325] [Chem. 40]

[0326]

[0327] Comparative Example 1 (Polymerization of non-fluorine-based resin 1)

[0328] In a glass ampoule of a capacity of 75 mL, 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 (manufactured by Nippon Oil & Fats Co., Ltd.) as a polymerization initiator, and 13 g of 2-butanone were added, and after repeating nitrogen substitution and pressure release, radical polymerization was performed under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C, and left for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was dropped into 500 mL of methanol to precipitate, and washed twice with 300 mL of methanol. Further, vacuum drying was performed at 30°C for 8 hours, whereby 4.6 g of the non-fluorine resin 1 (yield: about 81%) was obtained. The non-fluorine resin 1 was analyzed by FT-IR, and it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) / methyl methacrylate (non-fluorine unit) = 38 / 62 (mole %), and it was a copolymer represented by the following formula (24). 1 H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinkable group unit 1) / methyl methacrylate (non-fluorine unit) = 38 / 62 (mole %), and it was a copolymer represented by the following formula (24).

[0329] (non-fluorine resin 1)

[0330] [Chemical Formula 41]

[0331]

[0332] Synthesis Example 6 (Synthesis of photocrosslinkable monomer 6)

[0333] Under a nitrogen atmosphere, a 200 mL flask was charged with 2-hydroxyethyl methacrylate 6 g, triethylamine 5.3 g, and tetrahydrofuran 18 g, and mixed well. Separately, a glass bottle was charged with cinnamoyl chloride 8.7 g and tetrahydrofuran 26 g, and dissolved. Then, nitrogen was flowed into the flask charged with 2-hydroxyethyl methacrylate, triethylamine, and tetrahydrofuran, and the solution in which cinnamoyl chloride was dissolved was added dropwise using a dropping funnel, and stirred for 22 hours. Then, the salt as a byproduct was removed by filtration, and tetrahydrofuran was removed using an aspirator. Then, the product was dissolved in 50 g of toluene, washed three times with an aqueous sodium bicarbonate solution, and vacuum dried. The resulting substance after drying was analyzed by H-NMR and gas chromatography. 1 H-NMR and gas chromatography confirmed that it was a substance represented by the following formula (25) (photocrosslinkable monomer 6). (GC purity 91%)

[0334] (photocrosslinkable monomer 6)

[0335] [Chemical Formula 42]

[0336]

[0337] Comparative Example 2 (Polymerization production of fluorine resin 13)

[0338] In a glass ampoule of a capacity of 75 mL, 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 (manufactured by Nippon Oil & Fats Co., Ltd.) as a polymerization initiator, and 24 g of 2-butanone were added, nitrogen substitution and pressure release were repeated, and then heat sealing was performed under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C, and was allowed to stand for 24 hours, whereby radical polymerization was performed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise into methanol 500 mL to precipitate the polymer, and then the polymer was washed twice with methanol 300 mL. Further, vacuum drying was performed at 30°C for 8 hours, whereby 9.2 g of the fluorine-based resin 13 (yield: about 90%) was obtained. The fluorine-based resin 13 was analyzed by GPC, and the results are shown in Table 1. The GPC analysis was performed under the following conditions. 1 The composition was confirmed by1H-NMR measurement to be photocrosslinkable monomer 6 (photocrosslinkable group unit 6) / 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit) = 38 / 62 (mole %), and to be a copolymer represented by the following formula (26).

[0339] (Fluorine-based resin 13)

[0340] [Chemical Formula 43]

[0341]

[0342] Evaluation of solubility in fluorine-based solvents

[0343] Each of the synthesized fluorine-based resins 1 to 12 or non-fluorine-based resin 1 was added to each of the following fluorine-based solvents (Solvent 1 to Solvent 8) so as to be 3 wt%, and the temperature was increased to 50°C while mixing, and then the temperature was decreased to room temperature, and it was visually confirmed whether or not there was an insoluble component or a precipitated component. The results are shown in Table 1. In Table 1, the presence of an insoluble component or a precipitated component is indicated as "insoluble", and the absence of an insoluble component or a precipitated component is indicated as "soluble".

[0344] Solvent 1: 2H, 3H-decafluoropentane

[0345] Solvent 2: 1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane

[0346] Solvent 3: 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether

[0347] Solvent 4: hexafluorobenzene

[0348] Solvent 5: 2, 2, 3, 3-tetrafluoro-1-propanol

[0349] Solvent 6: 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1-pentanol

[0350] Solvent 7: 1H, 1H, 7H-dodecafluoro-1-heptanol

[0351] Solvent 8: 2,2,3,3,4,4,4-heptafluoro-1-butanol

[0352] It was confirmed that the fluorine-based resins 1 to 12 were dissolved in many fluorine-based solvents.

[0353] [Table 1]

[0354] Resin Solvent 1 Solvent 2 Solvent 3 Solvent 4 Solvent 5 Solvent 6 Solvent 7 Solvent 8 Example 1 Fluorine-based resin 1 Dissolved Dissolved Dissolved Dissolved Dissolved Dissolved Dissolved Dissolved Example 2 Fluorine-based resin 2 Dissolved Dissolved Dissolved Dissolved Insoluble Dissolved Dissolved Dissolved Example 3 Fluorine-based resin 3 Dissolved Dissolved Dissolved Dissolved Insoluble Dissolved Dissolved Dissolved Example 4 Fluorine-based resin 4 Dissolved Dissolved Dissolved Dissolved Insoluble Dissolved Dissolved Dissolved Example 5 Fluorine-based resin 5 Insoluble Dissolved Dissolved Dissolved Dissolved Dissolved Dissolved Dissolved Example 6 Fluorine-based resin 6 Insoluble Insoluble Insoluble Dissolved Dissolved Dissolved Dissolved Dissolved Example 7 Fluorine-based resin 7 Insoluble Dissolved Insoluble Dissolved Dissolved Dissolved Dissolved Insoluble Example 8 Fluorine-based resin 8 Insoluble Dissolved Insoluble Dissolved Dissolved Dissolved Dissolved Dissolved Example 9 Fluorine-based resin 9 Insoluble Insoluble Insoluble Dissolved Dissolved Dissolved Dissolved Dissolved Example 10 Fluorine-based resin 10 Insoluble Insoluble Insoluble Insoluble Dissolved Dissolved Dissolved Insoluble Example 11 Fluorine-based resin 11 Insoluble Insoluble Insoluble Dissolved Dissolved Dissolved Dissolved Dissolved Example 11 Fluorine-based resin 12 Dissolved Dissolved Dissolved Dissolved Insoluble Dissolved Dissolved Dissolved Comparative Example 1 Non-fluorine-based resin 1 Insoluble Insoluble Insoluble Insoluble Dissolved Dissolved Dissolved Dissolved

[0355] Evaluation of liquid repellency (water repellency / oil repellency)

[0356] A solution (3 wt%, solvent: propylene glycol monomethyl ether acetate) of the fluorine-based resins 1 to 11 or the non-fluorine-based resin 1 was spin-coated on a clean and dry 30 x 30 mm 2 glass substrate (Eagle XG, Corning) at 500 rpm x 5 seconds, 1500 rpm x 20 seconds. In the case where UV irradiation was performed, 500 mJ / cm 2 of ultraviolet rays was irradiated. The contact angles with respect to water, diiodomethane, m-xylene, and tetrahydronaphthalene were measured by the θ / 2 method using a contact angle meter (DM-300, Kyowa Interface Science Co., Ltd.). The results are shown in Table 2.

[0357] It was confirmed that the fluorine-based resins 1 to 12 had excellent liquid repellency. On the other hand, the non-fluorine-based resin 1 did not have excellent liquid repellency.

[0358] [Table 2]

[0359]

[0360] Evaluation of photocrosslinking (curing) property

[0361] A solution of the fluorine-based resins 1 to 11 or the fluorine-based resin 13 or a solution further containing a sensitizer (use of the solution is described in Table 3) was spin-coated on a clean and dry 30 x 30 mm 2 glass substrate (Eagle XG, Corning) using a spin coater so that the film thickness after drying became 100 to 150 nm, and the glass substrate was sufficiently dried. The fluorine-based resin was irradiated with 50 to 500 mJ / cm 2 of ultraviolet rays, and the resin film was photocrosslinked. The thickness of the film was measured using a Dektak XT probe-type profilometer (Bruker), and was set as To. Next, the glass plate coated with the photocrosslinked resin film was immersed in acetone, which is a good solvent for the fluorine-based resin, for 1 minute, taken out, dried at 100°C using a hot plate for 1 minute, and the film thickness after drying was measured, and was set as Ti. Using these film thickness measurement values, the residual film rate (R) was calculated by the following equation.

[0362] R = T1 / T0 x 100 (%)

[0363] The photo-crosslinking (curing) property was evaluated by taking the residual film rate (R) of 95% or more as a criterion for judging crosslinking. Note that the lower the UV irradiation amount at which the residual film rate reaches 95% or more, the higher (faster) the photo-crosslinking property. The photo-crosslinking property was evaluated by taking the residual film rate (R) of 95% or more at 500 mJ / cm 2 The case where the residual film rate (R) reached 95% or more at the following UV irradiation amounts was judged as "crosslinking", and the case where the residual film rate (R) did not reach 95% or more at 500 mJ / cm 2 The case where the residual film rate (R) did not reach 95% or more at the following UV irradiation amounts was judged as "insufficient crosslinking". The results are shown in Table 3:

[0364] Solvent 6: 2,2,3,3,4,4,5,5-octafluoro-l-pentanol

[0365] Solvent 9: Propylene glycol monomethyl ether acetate

[0366] Sensitizer 1: 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0367] [Table 3]

[0368]

[0369] <Pattern formation / evaluation of half-etching of semiconductor solution>

[0370] To form a pattern, the fluorine-based resins 1 to 11 or the non-fluorine-based resin 1 were dissolved in propylene glycol monomethyl ether acetate solvent to prepare a 3 wt% solution. As a mask for pattern formation, a mask patterned with chromium, in which 10 squares of 50 μm on one side were arranged longitudinally and 10 squares of 50 μm on one side were arranged transversely, was used. The above solution was spin-coated on a glass substrate of 100 x 100 mm 2 to obtain a film, and the mask was arranged on the film. UV of 300 mJ / cm 2 was irradiated. After the irradiation, the un-crosslinked portion was washed away with acetone for 1 minute, and it was confirmed with a laser microscope whether a pattern in which 100 holes of 50 x 50 μm 2 in size were left out was formed on the film.

[0371] Next, a half-coating evaluation of the semiconductor solution was performed. In the inside of the pattern (a region in which the fluorine-based resin 1 to 11 or the non-fluorine-based resin 1 was removed. The same applies hereafter.), a 0.8 wt% tetralin solution of the organic semiconductor represented by the above formula (D-11) (di-n-hexyl-dithienobenzodithiophene) was subjected to inkjet printing. After the printing, it was confirmed using a laser microscope whether the semiconductor solution had not wetted the outside of the pattern (a region in which the fluorine-based resin 1 to 11 or the non-fluorine-based resin 1 had not been removed) and formed a semiconductor layer in the inside of the pattern. The results are shown in Table 4. Note that the organic semiconductor represented by the formula (D-11) was synthesized according to the method described in Japanese Patent Laid-Open No. 2012-209329.

[0372] [Table 4]

[0373] Resin Pattern formation Evaluation of the semiconductor solution for the split coating Example 1 Fluorine-based resin 1 Formed Capable of split coating Example 2 Fluorine-based resin 2 Formed Capable of split coating Example 3 Fluorine-based resin 3 Formed Capable of split coating Example 4 Fluorine-based resin 4 Formed Capable of split coating Example 5 Fluorine-based resin 5 Formed Capable of split coating Example 6 Fluorine-based resin 6 Formed Capable of split coating Example 7 Fluorine-based resin 7 Formed Capable of split coating Example 8 Fluorine-based resin 8 Formed Capable of split coating Example 9 Fluorine-based resin 9 Formed Capable of split coating Example 10 Fluorine-based resin 10 Formed Capable of split coating Example 11 Fluorine-based resin 11 Formed Capable of split coating Comparative Example 1 Non-fluorine-based resin 1 Formed Incapable of split coating

[0374] Evaluation of Organic Transistor

[0375] (Formation of Gate)

[0376] A 100 x 100 mm 2 glass substrate was set in a sputtering device (Shibaura Mechatronics Co., Ltd., CFS-4EP-LL), silver was deposited in a manner of 50 nm, and then patterned by photolithography to form a silver electrode, i.e., a gate.

[0377] (Formation of Insulating Layer)

[0378] On the above substrate on which the gate was formed, an insulating layer was deposited using a poly-p-xylylene evaporation device (Parylene K.K., PDS 2010) in a manner such that the film thickness of the poly-p-xylylene C became about 500 nm.

[0379] (Formation of Source / Drain)

[0380] The substrate on which the above insulating layer was formed was set in a sputtering device, silver was deposited in a manner of 50 nm at 200 W, and then patterned by photolithography to form a source / drain having a channel length of 20 μm and a channel width of 50 μm.

[0381] (Pattern Formation of Liquid Repellency)

[0382] An acetic acid 2-methoxy-1-methylethyl ester solution (3 wt%) of each of the fluorine-based resins 1 to 11 was prepared, spin-coated onto the substrate on which the source / drain was formed in a manner such that the film thickness became about 100 nm, and dried at 100°C for 1 minute. Then, a mask having a light-shielding portion in the shape of a rectangle of 30 μm x 60 μm was aligned in a manner such that the center portion of the above light-shielding portion coincided with the center portion between the above source and drain, brought into contact with the substrate, and irradiated with 250 mJ / cm2 ultraviolet rays, thereby cross-linking the range other than the light shielding portion. After the substrate after the ultraviolet irradiation is washed with acetone for 1 minute and dried with nitrogen, the fluorine-based resin present in the light shielding portion of the mask is removed, and a liquid repellent pattern is formed.

[0383] (Electrode surface modification)

[0384] The substrate on which the source / drain electrode is formed is immersed in an isopropyl alcohol solution (30 mmol / L) of pentafluorothiophenol for 5 minutes, thereby modifying the surface of the electrode formed on the substrate.

[0385] (Preparation of an organic semiconductor layer formation solution)

[0386] In a 10-ml sample tube, 24 mg of the organic semiconductor represented by the above formula (D-11) (di-n-hexyl dithienobenzodithiophene), 3 mg of polystyrene (manufactured by Sigma-Aldrich, average Mw 280,000), and 2,973 mg of tetralin (manufactured by Sigma-Aldrich) were added under air, and the organic semiconductor and the polystyrene were dissolved by heating to 50°C, thereby preparing an organic semiconductor layer formation solution. Note that the organic semiconductor represented by formula (D-11) was synthesized according to the method described in Japanese Patent Application Publication No. 2012-209329.

[0387] (Formation of an organic semiconductor layer)

[0388] The organic semiconductor layer formation solution prepared above was filled into an ink cartridge of 10 pL of a basic droplet amount, and printed to the channel portion between the source / drain electrodes after the electrode modification using an inkjet device (DMP-2831, manufactured by FUJIFILM Dimatix), and dried on a hot plate at 90°C for 10 minutes, thereby forming an organic semiconductor layer, and an organic transistor was fabricated.

[0389] (Result of electrical characteristics)

[0390] For the fabricated organic transistor, the voltage between the source / drain electrodes (Vd) was set to -15 V, and the gate voltage (Vg) was scanned, and the transfer characteristics (Id-Vg) before the application of a bias voltage were measured. As a result, the mobility was 0.5 to 0.7 cm 2 / V·s, and an excellent mobility was exhibited.

[0391] <Evaluation of damage to the organic semiconductor>

[0392] To the fluorine-based resin 1 obtained in Example 1, 4,4'-bis(diethylamino)benzophenone was added as a sensitizer, and dissolved in 2,2,3,3,4,4,5,5-octafluoro-l-pentanol solvent to prepare a solution (fluorine-based resin 15 wt%, sensitizer 0.4 wt%). Using this solution, a protective film of about 2 μm was formed by spin coating on the organic semiconductor layer of the above organic transistor. Then, a mask having a light shielding portion was brought into contact with the substrate on which the protective film was formed, and ultraviolet rays of 300 mJ / cm2were irradiated to cure it. Further, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether was used as a fluorine-based solvent to remove the fluorine-based resin present in the light shielding portion of the above mask to form a pattern. As a result, the change in mobility before and after the formation of the protective film was 5% or less, and no damage was caused to the organic semiconductor. 2

[0393] BRIEF DESCRIPTION OF DRAWINGS

[0394] 1 Organic semiconductor layer

[0395] 2 Substrate

[0396] 3 Gate

[0397] 4 Gate insulating layer

[0398] 5 Source

[0399] 6 Drain

[0400] 7 Pattern

[0401] 8 Protective film layer​

Claims

1. A fluorine-based resin having a repeating unit represented by the following formula (1) containing a photocrosslinkable group and a repeating unit containing a fluorine atom represented by the following formula (3), Formula (1) wherein, R1 represents a hydrogen atom or a methyl group; L1 represents -C(=0)0-; and A represents a linking group represented by the following formula (a-1): Formula (a-1) wherein, *L represents a bonding position with L1 in the above formula (1), and the preceding * of the carbon atom represents a bonding position with an oxygen atom constituting an ester group in the above formula (1); R2, R3, R4, R5, and R6 are the same or different and represent one selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and a linear fluoroalkyl group having 1 to 4 carbon atoms; and n is 2. ; 2. The fluorine-based resin according to claim 1, wherein the repeating unit represented by the above formula (1) is contained in an amount of 10 to 90% by mass.

3. The fluorine-based resin according to claim 1 or 2, wherein the repeating unit represented by the above formula (3) is contained in an amount of 10 to 90% by mass.

4. The fluorine-based resin according to any one of claims 1 to 3, wherein the repeating unit represented by the following formula (2) is further contained: Formula (2) wherein, R7 represents a hydrogen atom or a methyl group; and R8 represents an alkyl group having 1 to 30 carbon atoms.

5. The fluorine-based resin according to any one of claims 1 to 4, wherein the fluorine-based resin is soluble in a fluorine-based solvent. ; 6. A composition comprising the fluorine-based resin according to any one of claims 1 to 5, and at least one solvent selected from an organic solvent and a fluorine-based solvent.

7. A photocrosslinking product of the fluorine-based resin according to any one of claims 1 to 5 or the composition according to claim 6.

8. A pattern composed of the photocrosslinking product according to claim 7. ; 9. An electronic device provided with the photocrosslinking product according to claim 7. ​ ​ ​ 2. The fluorine-based resin according to claim 1, wherein ​ ; ​ 3. The fluorine-based resin according to claim 1 or 2, wherein, ​ ​ ​ ​ ​

Images