Resin, composition, photocrosslinked product, pattern, and electronic device provided with same

Abstract

The purpose of one embodiment of the present invention is to provide a resin which has liquid repellency, is highly soluble in alkali liquor, and does not dissolve in a solvent by photocrosslinking under low exposure. A resin according to one embodiment of the present invention contains: a repeating unit represented by formula (1) and containing a photocrosslinkable group; and one or more units selected from the group consisting of a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group. In formula (1), R1 represents hydrogen or a methyl group, L1 represents a single bond or a linking group, A represents a linking group, and R2-R6 represent one selected from the group consisting of hydrogen, a halogen, an alkyl group, a haloalkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and an amino group. # imgabs0 #

Description

Technical Field

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

[0002] In recent years, technical development related to the manufacture of organic electronic devices based on a low-cost and highly productive all-printing method has been actively carried out. As an electronic device, the development of an organic transistor, for example, is also being promoted. The organic transistor is manufactured through a plurality of processes, including the following process: a protective film composed of a resin protects the organic transistor and forms a pattern of an EL light-emitting portion. For example, the pattern is set to cover the source electrode, the drain electrode and the organic semiconductor layer or the polymer layer, and does not exist on the electrode forming the EL light-emitting portion.

[0003] Generally, the EL light-emitting portion is formed using photolithography, which is a technique for exposing a substrate surface coated with a photosensitive material (resist) to a pattern through a photomask or a reticle, etc., to form a pattern consisting of exposed portions and unexposed portions. In the photolithography, the EL light-emitting portion is opened by dry etching or wet etching.

[0004] As a pattern forming material, a photoreactive polymer material is used. In a coating method such as the full printing method, the material is applied in the form of ink dissolved in a solvent, and after drying and removing the solvent, the material is made insoluble in the solvent by photocrosslinking reaction to form a pattern. Therefore, the polymer material used in the coating method such as the full printing method is required to have both excellent solubility in the solvent and the property that the material can undergo photocrosslinking reaction by exposure at room temperature and for a short time after removing the solvent.

[0005] Here, a method for manufacturing an organic electric field light-emitting element included in an organic electric field display and an organic electric field lighting is shown. First, the above-mentioned polymer material is applied on a substrate, and the portion where the pattern is to be formed is subjected to a photo-crosslinking reaction, and the portion where the photo-crosslinking reaction is not carried out is removed. Thus, the remaining portion becomes a pattern. Various functional layers are stacked on the portion (inside the pattern) where the polymer material is removed. The technology of forming the functional layer using ink-like raw materials is promising, but from the viewpoint of ink adhering to the inside of the pattern and preventing ink from leaking to the outside of the region beyond the portion (outside the pattern) where the polymer material is not removed, it is expected that the material constituting the pattern has liquid repellency. In addition, when manufacturing an organic electric field light-emitting element, alkali solution is mostly used, and solubility in alkali solution is required.

[0006] As such a material, in Patent Document 1, a negative photosensitive resin composition having high photoreactivity, capable of patterning with alkali solution, and capable of forming a coating having liquid repellency and a photocurable pattern made therefrom can be cited. However, since the resin of the composition does not have photocurability, it is necessary to perform heat curing at high temperature for a long time after patterning. High temperature and long-term treatment is the cause of the performance degradation of electronic devices and the selection restriction of plastic substrates. Therefore, in order to prevent the performance degradation of electronic devices, it is required to develop a fluorine-based material capable of photocrosslinking.

[0007] As such a technique, there is a method of forming a pattern using a resin soluble in a fluorine-based solvent, which is disclosed in Patent Document 2 and Non-Patent Document 1. However, this resin has a problem that it does not undergo photo-crosslinking.

[0008] Examples of the photo-crosslinkable resin include resins such as those disclosed in Non-Patent Document 2 that use an anthracene crosslinking group.

[0009] Prior art literature Patent Literature Patent Document 1: Japanese Patent No. 5932512 Patent Document 2: Japanese Patent No. 6281427 Non-patent literature Non-patent document 1: Appl. Phys. Express 7, 101602 (2014) Non-patent document 2: J Polym Sci A Polym Chem 53, 1252 (2015) Summary of the invention

[0010] Technical problem to be solved by the invention However, the resin described in Non-Patent Document 2 has low photo-crosslinking properties and requires a high exposure dose. In addition, it is not soluble in alkaline solution. Therefore, a resin having high photoreactivity and solubility in alkaline solution is required.

[0011] The present invention has been made in view of the above technical problems, and an object of the present invention is to provide a resin which has liquid repellency, is soluble in an alkali solution, and can be photo-crosslinked at a low exposure dose without being dissolved in a solvent.

[0012] Technical solutions for solving technical problems The present inventors have conducted intensive studies to solve the above-mentioned technical problems and have found that a resin having a specific structure can solve the above-mentioned technical problems, thereby completing the present invention.

[0013] Specifically, the resin according to one embodiment of the present invention contains a repeating unit represented by the following formula (1) containing a photo-crosslinkable group, and one or more units selected from a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group.

[0014] [Chemistry 1]

[0015] In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, A represents an m-valent linking group, R2, R3, R4, R5 and R6 are the same or different and 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 greater than 3, and n represents an integer of m-1.

[0016] Effects of the Invention According to the present invention, a resin having liquid repellency, being soluble in an alkali solution and being insoluble in a solvent by photocrosslinking at a low exposure dose can be obtained. The resin can be used for pattern formation, and by using the resin for pattern formation, it is possible to prevent the performance of the obtained electronic device from being degraded. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a diagram showing a cross-sectional shape of an organic transistor.

[0018] Figure 2 This is a diagram showing a cross-sectional shape of an organic transistor which is one embodiment of the electronic device of the present invention. DETAILED DESCRIPTION

[0019] Hereinafter, the resin which is one embodiment of the present invention will be described in detail.

[0020] The resin of the present invention is a resin containing the following units: The repeating unit represented by the following formula (1), and One or more units selected from the group consisting of a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group.

[0021] [Chemistry 2]

[0022] The above formula (1) in the resin of the present invention has a photo-crosslinkable group. As a result, the resin exhibits high photoreactivity, and in a film obtained by coating the resin, only the light-irradiated portion can be selectively insolubilized.

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

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

[0025] The divalent linking group in L1 is preferably a divalent linking group formed by combining at least two groups selected from a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-). Thus, a flat and crack-free film can be formed.

[0026] Specific examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.

[0027] Specific examples of the branched alkylene group having 3 to 10 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.

[0028] Specific examples of the cyclic alkylene group having 3 to 10 carbon atoms include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like, among which cyclohexylene is preferred.

[0029] Specific examples of the arylene group having 6 to 12 carbon atoms include phenylene, xylylene, biphenylene, naphthylene, and 2,2′-methylenebiphenylene. Among them, phenylene is preferred.

[0030] Among these divalent linking groups, an ester bond (—C(═O)O—) formed by combining a carbonyl group and an ether group or a linking group formed by combining a phenylene group and an ether group is more preferred, and (—C(═O)O—) is even more preferred.

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

[0032] m represents an integer of 3 or more, is preferably an integer of 3 to 5, is more preferably an integer of 3 to 4, and is further preferably 3.

[0033] From the viewpoint of improving the solubility of the obtained resin in organic solvents and fluorine-based solvents, A may be an m-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent.

[0034] Examples of the substituent that the m-valent hydrocarbon group A may have include an alkyl group, an alkoxy group, a halogen atom, and a hydroxyl group.

[0035] As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and cyclohexyl, is more preferred, an alkyl group having 1 to 4 carbon atoms is further preferred, and a methyl or ethyl group is particularly preferred.

[0036] The alkoxy group includes, for example, an alkoxy group having 1 to 16 carbon atoms and having a linear or branched alkyl group, such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, an isobutoxy group, a n-pentoxy group, a n-hexoxy group, an isohexoxy 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 preferred are groups 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.

[0037] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom or a chlorine atom is preferred.

[0038] Among them, the m-valent hydrocarbon group A is preferably a linking group selected from the following formulae (a-1) to (a-4).

[0039] [Chemistry 3]

[0040] In formulas (a-1) to (a-4), In the above formula (1), the bonding position with L1 is represented by the front end of the carbon atom. It represents the bonding position to the oxygen atom constituting the ester group in the above formula (1).

[0041] From the perspective of ease of reaction in monomer synthesis, the m-valent hydrocarbon group A is preferably a trivalent linking group selected from one of formula (a-1), formula (a-2), and formula (a-3), more preferably a trivalent linking group of formula (a-1) or formula (a-2), and even more preferably a trivalent linking group of formula (a-1).

[0042] In 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 straight-chain 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 straight-chain 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.

[0043] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom or a chlorine atom is preferred.

[0044] As the linear alkyl group having 1 to 20 carbon atoms, a linear alkyl group having 1 to 6 carbon atoms is preferred, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. Among them, a methyl group or an ethyl group is preferred.

[0045] The branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 6 carbon atoms, and specific examples thereof include an isopropyl group and a tert-butyl group.

[0046] The cyclic alkyl group having 3 to 20 carbon atoms is preferably a cyclic alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Among them, a cyclohexyl group is preferred.

[0047] The linear halogenated alkyl group having 1 to 20 carbon atoms is preferably a linear fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group. Among them, a trifluoromethyl group is preferred.

[0048] The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 8 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group.

[0049] The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include phenyl, α -methylphenyl, naphthyl, etc., among which phenyl is preferred.

[0050] The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenoxy group and a 2-naphthoxy group. Among them, a phenoxy group is preferred.

[0051] Examples of the amino group include a primary amino group (-NH2); a secondary amino group such as a methylamino group; and a tertiary amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, and a group bonded to a nitrogen atom of a nitrogen-containing heterocyclic compound (such as pyrrolidine, piperidine, piperazine, etc.).

[0052] From the reason of further improving the solubility, photocurability and liquid repellency of the resin in fluorine-based solvents, R2, R3, R4, R5 and R6 are each independently preferably one selected from a hydrogen atom, an alkyl group, a halogen atom and a linear halogenated alkyl group having 1 to 20 carbon atoms, and a hydrogen atom is more preferably used.

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

[0054] [Chemistry 4]

[0055] [Chemistry 5]

[0056] [Chemistry 6]

[0057] [Chemistry 7]

[0058] [Chemistry 8]

[0059] The resin of the present invention may contain one or more units selected from the group consisting of a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group.

[0060] From the viewpoint of liquid repellency, the resin of the present invention may contain a repeating unit containing a fluorine atom, and thereby, layer separation is easily caused in a film obtained by coating a composition with the resin.

[0061] The repeating unit containing a fluorine atom is preferably a repeating unit represented by the following formula (2).

[0062] [Chemistry 9]

[0063] In formula (2), R7 represents a hydrogen atom or a methyl group.

[0064] In formula (2), L2 represents a single bond or a divalent linking group.

[0065] The divalent linking group in L2 is preferably a divalent linking group formed by combining at least two groups selected from a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-). Thus, a flat and crack-free film can be formed.

[0066] Specific examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.

[0067] Specific examples of the branched alkylene group having 3 to 10 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.

[0068] Specific examples of the cyclic alkylene group having 3 to 10 carbon atoms include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like, among which cyclohexylene is preferred.

[0069] Specific examples of the arylene group having 6 to 12 carbon atoms include phenylene, xylylene, biphenylene, naphthylene, and 2,2′-methylenebiphenylene. Among them, phenylene is preferred.

[0070] Among these divalent linking groups, an ester bond (—C(═O)O—) formed by combining a carbonyl group and an ether group or a linking group formed by combining a phenylene group and an ether group is more preferred, and (—C(═O)O—) is even more preferred.

[0071] In formula (2), Rf1 represents one selected from 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.

[0072] When Rf1 is a fluoroalkyl group, the resin according to one embodiment of the present invention exhibits affinity for fluorine-based solvents and liquid repellency.

[0073] When Rf1 is a linear fluoroalkyl group, specific examples of Rf1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or an alkyl group having 10 to 14 carbon atoms substituted with a fluorine atom. When the bonding element to Rf1 in L2 is oxygen, the substitution position of the fluorine atom in Rf1 may be on a carbon atom other than the carbon atom directly bonded to oxygen in L2.

[0074] When Rf1 is a linear fluoroalkyl group, Rf1 is preferably a group represented by the following formula (3).

[0075] [Chemistry 10]

[0076] In formula (3), represents the bonding position with L2 in formula (2).

[0077] In formula (3), X is a hydrogen atom or a fluorine atom.

[0078] In formula (3), y is an integer of 1-4, preferably 1-2.

[0079] In formula (3), z is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

[0080] When Rf1 is a group represented by the formula (3), synthesis of a monomer serving as a raw material of the repeating unit represented by the formula (2) becomes easier.

[0081] When Rf1 is a branched fluoroalkyl group, specific examples of Rf1 include 1,1,1,3,3,3-hexafluoroisopropyl, 1-(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl, 1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl, and 1,1-bis(trifluoromethyl)ethyl.

[0082] When Rf1 is a cyclic fluoroalkyl group, specific examples of Rf1 include 1,2,2,3,3,4,4,5,5-nonafluorocyclopentyl and 1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl.

[0083] The repeating unit represented by the above formula (2) is preferably a repeating unit represented by the following formula (4).

[0084] [Chemistry 11]

[0085] In formula (4), R8 represents either a hydrogen atom or a methyl group.

[0086] In formula (4), X is a hydrogen atom or a fluorine atom.

[0087] In formula (4), y is an integer of 1-4, preferably 1-2.

[0088] In formula (4), z is an integer of 1-14, preferably 2-10, and more preferably 4-8.

[0089] The resin involved in one embodiment of the present invention may contain one repeating unit represented by the above formula (2), or may contain two or more repeating units. For example, it may contain two repeating units, namely, a repeating unit having the above straight-chain fluoroalkyl group as Rf1, and a repeating unit having the above branched fluoroalkyl group as Rf1, or may contain two or more repeating units having straight-chain fluoroalkyl groups with different carbon atoms. The resin involved in one embodiment of the present invention preferably contains one repeating unit represented by the formula (2).

[0090] Specific examples of the repeating unit containing a fluorine atom in the resin according to one embodiment of the present invention include one selected from the repeating units represented by the following formulae (C-1) to (C-33).

[0091] [Chemistry 12]

[0092] [Chemistry 13]

[0093] [Chemistry 14]

[0094] The repeating unit containing a fluorine atom is preferably one selected from the repeating units represented by the above formulae (C-1) to (C-33), further preferably one selected from the repeating units represented by the formulae (C-9) to (C-33), particularly preferably one selected from the repeating units represented by the formulae (C-14) to (C-21) or one selected from the repeating units represented by the formulae (C-27) to (C-33).

[0095] From the viewpoint of expressing solubility in an alkaline solution, the resin of the present invention may contain at least one of a repeating unit containing an acidic functional group and a repeating unit containing a hydrophilic functional group.

[0096] Specifically, at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group preferably has a repeating unit containing a functional group selected from a carboxyl group, a sulfonic group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group and a cyano group, and more preferably a repeating unit containing a carboxyl group.

[0097] At least one of the repeating units containing acidic functional groups and the repeating units containing hydrophilic functional groups can be used alone, or two or more thereof can be used in combination. It should be noted that when the repeating units containing acidic functional groups and the repeating units containing hydrophilic functional groups are identical to each other in chemical structural formula, the two are combined and counted as one. In addition, the repeating units used may be repeating units containing acidic and hydrophilic functional groups, or may be repeating units containing both acidic but non-hydrophilic functional groups and hydrophilic but non-acidic functional groups.

[0098] At least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group is preferably a repeating unit represented by the following formula (a).

[0099] [Chemistry 15]

[0100] In formula (a), R9 represents a hydrogen atom or a methyl group, and L3 represents a single bond or a divalent linking group.

[0101] The divalent linking group in L3 is preferably a divalent linking group formed by combining at least two groups selected from a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-). Thus, a flat and crack-free film can be formed.

[0102] Specific examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.

[0103] Specific examples of the branched alkylene group having 3 to 10 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.

[0104] Specific examples of the cyclic alkylene group having 3 to 10 carbon atoms include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like, among which cyclohexylene is preferred.

[0105] Specific examples of the arylene group having 6 to 12 carbon atoms include phenylene, xylylene, biphenylene, naphthylene, and 2,2′-methylenebiphenylene. Among them, phenylene is preferred.

[0106] Among these divalent linking groups, an arylene group having 6 to 12 carbon atoms is more preferred, and a phenylene group is further preferred.

[0107] As L3, a single bond or an arylene group having 6 to 12 carbon atoms is more preferred, and a single bond or a phenylene group is further preferred.

[0108] Specifically, the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group in the resin according to one embodiment of the present invention may be one selected from the repeating units represented by the following formulae (D-1) to (D-23), wherein (D-1) to (D-2) and (D-19) to (D-23) satisfying formula (a) are preferred, (D-1) to (D-2) and (D-20) to (D-22) are more preferred, and (D-1) and (D-22) are more preferred.

[0109] In the following formula, R9 is a hydrogen atom or a methyl group.

[0110] [Chemistry 16]

[0111] From the viewpoint of improving solubility in alkaline solution and more efficiently performing photocuring, the resin according to one embodiment of the present invention preferably contains 5 mol % to 50 mol %, preferably 5 mol % to 40 mol %, of the repeating unit represented by the formula (1).

[0112] The resin according to one embodiment of the present invention preferably contains 5 mol % to 50 mol %, preferably 5 mol % to 40 mol %, and preferably 5 mol % to 30 mol %, of a repeating unit containing a fluorine atom.

[0113] The resin according to one embodiment of the present invention preferably contains 20 mol % to 90 mol %, preferably 30 mol % to 90 mol %, and preferably 30 mol % to 80 mol %, of a repeating unit containing an acidic functional group.

[0114] The resin according to one embodiment of the present invention preferably contains 20 mol % to 90 mol %, preferably 30 mol % to 90 mol %, and preferably 30 mol % to 80 mol %, of a repeating unit containing a hydrophilic functional group.

[0115] The resin according to one embodiment of the present invention may contain other monomer repeating units within the scope of the present invention. Examples of other monomer repeating units include olefin residue units such as ethylene residue units, propylene residue units, and 1-butene residue units; styrene residue units, α -vinyl aromatic hydrocarbon residue units such as methylstyrene residue units; carboxylic acid vinyl ester residue units such as vinyl acetate residue units, vinyl propionate residue units, and vinyl pivalate residue units; vinyl ether residue units such as methyl vinyl ether residue units, ethyl vinyl ether residue units, and butyl vinyl ether residue units; N-substituted maleimide residue units such as N-methylmaleimide residue units, N-cyclohexylmaleimide residue units, and N-phenylmaleimide residue units; acrylonitrile residue units; methacrylonitrile residue units; silicone residue units, etc.

[0116] The molecular weight of the resin of the present invention is not limited at all, and for example, a resin of 2000 to 10,000,000 (g / mol) can be used. From the viewpoint of solution viscosity and mechanical strength of the obtained resin, it is preferably 10,000 to 1,000,000 (g / mol).

[0117] The method for synthesizing the resin of the present invention is not particularly limited, and the resin can be synthesized, for example, by mixing monomers forming the repeating unit represented by the above formula (1), monomers forming the repeating unit containing the above fluorine atom, monomers forming the repeating unit containing an acidic functional group, monomers forming the repeating unit containing a hydrophilic functional group, and monomers forming any other repeating unit, and polymerizing them in an organic solvent using a free radical polymerization initiator.

[0118] The resin of the present invention is preferably soluble in alkaline solution.

[0119] The alkali solution is described below.

[0120] The alkaline solution is preferably an aqueous solution of an alkali containing at least one of inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines, quaternary ammonium salts, and cyclic amines.

[0121] Examples of the inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.

[0122] Examples of the primary amines include ethylamine and n-propylamine.

[0123] Examples of the secondary amines include diethylamine and di-n-butylamine.

[0124] Examples of the tertiary amines include triethylamine and methyldiethylamine.

[0125] Examples of the alcoholamines include dimethylethanolamine and triethanolamine.

[0126] Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.

[0127] Examples of the cyclic amines include pyrrole and piperidine.

[0128] Among them, as the alkali solution, inorganic bases, tertiary amines, alcohol amines, quaternary ammonium salts and the like are preferred, and quaternary ammonium salts are particularly preferred.

[0129] The hydrogen ion concentration index of the alkaline solution is preferably pH 8 or higher, more preferably pH 10 or higher, and even more preferably pH 12 or higher.

[0130] Hereinafter, a composition which is one embodiment of the present invention will be described.

[0131] A composition according to one embodiment of the present invention contains at least one solvent of an organic solvent and a fluorine-based solvent, and a resin.

[0132] The fluorine-based solvent can dissolve the resin of the present invention. By using a fluorine-based solvent as a solvent for dissolving the resin, when electronic devices are manufactured using a full printing method, damage to device components mainly composed of organic matter can be minimized, and the performance of the electronic device can be fully utilized.

[0133] In the fluorine compound constituting the fluorine-based solvent, the fluorine atom content is 50 mass % or more and 70 mass % or less relative to the gross mass of the fluorine-based compound, more preferably 55 mass % or more and 70 mass % or less. If it exceeds 70 mass %, the above-mentioned resin cannot be fully dissolved. In addition, if it is less than 50 mass %, when coating or printing on an organic semiconductor film, the surface of the organic semiconductor film may be dissolved or swollen.

[0134] As the fluorine-containing solvent contained in the composition of the present invention, the fluorine-containing hydrocarbons, fluorine-containing ethers or fluorine-containing alcohols shown below can be preferably used, and the fluorine-containing hydrocarbons or fluorine-containing ethers can be more preferably used.

[0135] Fluorinated hydrocarbons have low ozone depletion coefficients and are preferred as fluorinated solvents contained in the composition of the present invention. In particular, fluorinated hydrocarbons in which at least one hydrogen atom in a linear, branched or cyclic hydrocarbon having 4 to 8 carbon atoms is substituted with a fluorine atom are preferred because they are easy to apply.

[0136] As such fluorine-containing hydrocarbons, specifically, fluorine-containing hydrocarbons in which at least one of the hydrogen atoms of butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane or benzene is substituted with a fluorine atom can be exemplified. Specifically, fluorine-containing hydrocarbons such as 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 2H,3H-decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, hexafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane and hexafluorobenzene can be exemplified.

[0137] The boiling point of the fluorine-containing hydrocarbon is preferably 200° C. or lower, more preferably 180° C. or lower. When the boiling point of the fluorine-containing hydrocarbon is 200° C. or lower, the fluorine-containing hydrocarbon can be easily evaporated and removed by heating.

[0138] Among the above-mentioned fluorine-containing hydrocarbons, the following can be exemplified as examples having particularly preferred boiling points.

[0139] Examples include 2H,3H-decafluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and hexafluorobenzene.

[0140] In addition, from the perspective of low ozone depletion coefficient, fluorinated ethers can be used as fluorinated solvents. In particular, the boiling point of the fluorinated ether is preferably 200° C. or less, and more preferably 180° C. or less. If the boiling point of the fluorinated ether is 200° C. or less, the fluorinated ether can be easily evaporated and removed from the resin film by heating.

[0141] Preferred examples of the fluorine-containing ether include 1,1,2,3,3,3-hexafluoro-1-(2,2,2-trifluoroethoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3,3-pentafluoropropoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3-tetrafluoropropoxy)propane, 2,2,3,3,3-pentafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane, 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane, methyl perfluorobutyl ether, or ethyl nonafluorobutyl ether.

[0142] Examples of the fluorine-containing ether having a preferred boiling point include ethyl nonafluorobutyl ether, methyl perfluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, (1,1,1,2,3,3-hexafluoropropoxy)pentane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, and methoxyperfluoroheptene.

[0143] As the fluorine-containing 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. When the boiling point of the fluorine-containing alcohol is 200° C. or lower, the fluorine-containing alcohol can be easily removed by heating and evaporation.

[0144] Preferred examples of fluorine-containing alcohols include 1H,1H-trifluoroethanol, 1H1H-pentafluoropropanol, 1H,1H-heptafluorobutanol, 2-(perfluorobutyl)ethanol, 3-(perfluorobutyl)propanol, 2-(perfluorohexyl)ethanol, 3-(perfluorohexyl)propanol, 1H,1H,3H-tetrafluoropropanol, 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol, 2H-hexafluoro-2-propanol, and 1H,1H,3H-hexafluorobutanol.

[0145] Furthermore, in order to further improve the solubility of the resin, the composition according to one embodiment of the present invention may contain two or more fluorine-based solvents.

[0146] The organic solvent used in the composition of the present invention refers to an organic solvent that is not a fluorine-based solvent. As an organic solvent, there is no limitation as long as it can dissolve the resin of the present invention, and examples thereof include: hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-Butyrolactone, 1,3-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, tetradecahydrophenanthrene, 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, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, limonene, etc. In order to obtain a film with preferred properties, it is suitable to use an organic solvent with high solubility for dissolving the resin, preferably xylene and propylene glycol monomethyl ether acetate. In addition, a mixed solvent obtained by mixing two or more of the above solvents in an appropriate ratio can also be used.

[0147] The composition of a resin and at least one solvent selected from organic solvents and fluorinated solvents according to one embodiment of the present invention preferably contains 1 wt % to 50 wt % of the resin and 50 wt % to 99 wt % of the solvent.

[0148] In addition, the composition according to one embodiment of the present invention may contain a photosensitizer. The photosensitizer may be any agent that promotes the crosslinking reaction of the photo-crosslinkable group.

[0149] Examples of photosensitizers include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like; carbonyls such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzil; diphenyl monosulfide, diphenyl disulfide, tetramethylthiuram disulfide, and the like. disulfide) and other organic sulfides; acetophenone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methoxybenzophenone, 2,4,6-trimethoxybenzophenone and other benzophenones; p-toluenesulfonyl chloride, 1-naphthalenesulfonyl chloride, 1,3-benzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, p-acetamidobenzenesulfonyl chloride and other sulfonyl halides; 5-nitrofluorene, 5-nitroacenaphthene, N-ethyl Aromatic nitro compounds such as acyl-4-nitro-1-naphthylamine and beclamide; coumarins such as 7-diethylamino-3-thiophenoylcoumarin and 3,3′-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, azobisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; pigments such as ethionine, thionine, and methylene blue. By adding a photosensitizer, the resin involved in one embodiment of the present invention can be crosslinked (insolubilized) at a lower exposure amount. In addition, the sensitizer can be used in combination of two or more as needed.

[0150] The composition of a resin, a photosensitizer, and at least one solvent selected from an organic solvent and a fluorine-based solvent involved in one embodiment of the present invention preferably contains 1 wt% to 50 wt% of the resin, 50 wt% to 99 wt% of the solvent, and 0.001 wt% to 5 wt% of the photosensitizer.

[0151] Hereinafter, a pattern which is one embodiment of the present invention will be described.

[0152] The resin of the present invention can be used to form a pattern. More specifically, a photocrosslinked product is obtained using the resin of the present invention or a composition thereof to form a pattern. Here, a cured product formed by photocrosslinking the resin of the present invention or a composition thereof, i.e., a photocrosslinked product, is also one embodiment of the present invention.

[0153] First, a resin coating is formed on the surface of a substrate by a known coating formation method. Examples of the substrate include various glass plates; polyesters such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; thermoplastic plastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide; epoxy resins; polyester resins; and thermosetting plastic sheets such as poly(meth)acrylic resins.

[0154] As a method for forming a coating film, for example, spin coating, drop coating, dip coating, doctor-blade coating, pad printing, squeegee coating, roll coating, rod coating, air knife coating, wire bar coating, flow coating, gravure printing, flexographic printing, super flexographic printing, screen printing, inkjet printing, letterpress reverse printing, reverse offset printing, adhesion reverse printing, etc. can be used.

[0155] Next, the coating is dried. The solvent evaporates during drying, and a non-sticky coating is obtained. The drying conditions vary depending on the boiling point and mixing ratio of the solvent used, and are preferably used in a wide range of about 50°C to 150°C and 10 to 2000 seconds.

[0156] When forming a coating film, when a coating film having a predetermined shape, that is, a shape identical to a target pattern, is formed by a printing method, the coating film having the predetermined shape is photo-crosslinked by exposure to light, and a photo-crosslinked product is obtained and fixed to form a pattern.

[0157] On the other hand, when a coating film having a predetermined shape is not formed during coating film formation, a pattern can be formed from the coating film using photolithography. When using photolithography, first, the dried coating film is exposed to light through a mask having a predetermined shape, i.e., a shape that can form a target pattern, to make it photo-crosslinked.

[0158] When curing the resin of the present invention by photocrosslinking, radiation such as ultraviolet rays and visible light can be used, and examples thereof include ultraviolet rays with a wavelength of 245 nm to 435 nm. The irradiation amount can be appropriately changed depending on the composition of the resin, and for example, 10 mJ / cm 2 ~5000mJ / cm 2 From the viewpoint of preventing the decrease of the crosslinking degree and improving the economic efficiency by shortening the process time, the irradiation dose is preferably 100 mJ / cm 2 ~4000mJ / cm 2 Specific examples of light irradiation devices or light sources include germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultrahigh-pressure mercury lamps, electrodeless lamps, and metal halide lamps.

[0159] The irradiation with ultraviolet rays is usually carried out in the atmosphere, but can also be carried out in an inert gas or under a stream 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 carried out using a developer to remove the unexposed portion. As the developer, any solvent can be used as long as it is an alkaline solution or an organic solvent that dissolves the uncured resin. For example, the above-mentioned alkaline solution; aromatic solvents such as benzene, toluene, and xylene; ether solvents such as dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate; fluorine solvents 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-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H,7H-dodecafluoro-1-heptanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, etc.

[0160] The development time is preferably 30 to 300 seconds. In addition, the development method can be any one of the liquid covering method (Japanese: 液盛り法), immersion method, etc. After development, cleaning is carried out using a solvent, and air drying is carried out using compressed air or compressed nitrogen to remove the solvent on the substrate. Then, a heating treatment is carried out for 5 to 90 minutes at 40°C to 150°C using a heating device such as a hot plate or an oven to form a pattern.

[0161] After forming the pixel pattern through the above-mentioned photolithography process, it is also possible to remove the dirt on the surface of the substrate within the pixel. For example, irradiation with short-wavelength ultraviolet rays such as a low-pressure mercury lamp or an excimer UV, or optical ashing treatment, etc. can be cited to clean the surface of the substrate. Optical ashing treatment refers to a treatment of irradiating short-wavelength ultraviolet rays in the presence of ozone gas. The short-wavelength ultraviolet rays refer to light having a main peak at a wavelength of 100 nm to 300 nm.

[0162] When the liquid repellency is reduced after removing the dirt on the surface of the substrate within the above-mentioned pixel, the liquid repellency can also be restored by heat treatment or the like.

[0163] Thus, the resin of the present invention is itself soluble in an alkaline solution or an organic solvent, and through light irradiation, the photocrosslinkable groups possessed by the side chains are crosslinked and cured, and become insoluble in the solvent used. Utilizing this property, when the resin of the present invention is crosslinked by light irradiation, it can be used as a negative resist formed by removing the portion not irradiated with light by an alkaline solution or an organic solvent.

[0164] After patterning using the resin of the present invention, in order to prevent wetting and spreading of ink for forming a functional layer, the contact angle of the portion where the resin remains after crosslinking (outside the pattern) with respect to the ink is preferably 40° or more, more preferably 50° or more.

[0165] The resin of the present invention can be made into a protective film by the same method as the pattern, such as a coating film forming method, photocrosslinking, and development.

[0166] The resin of the present invention has excellent liquid repellency and can be used as a pattern material when manufacturing an organic transistor element, a color filter, or an organic EL element. In addition, the resin of the present invention can be used for electronic devices including the above-mentioned organic transistor element, color filter, or organic EL element.

[0167] Hereinafter, an electronic device which is one embodiment of the present invention will be described in detail.

[0168] The resin of the present invention can be used in electronic devices, and more specifically, can be used in electronic devices having a photocrosslinked product, which is a photocrosslinked product of a composition comprising the resin of the present invention and at least one solvent selected from organic solvents and fluorine-based solvents. Examples of the electronic device include organic transistors.

[0169] 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 electrode, a drain electrode, and a gate electrode. An example of the element structure of an organic transistor is shown as a cross-sectional diagram. Figure 1 1001 is a bottom gate-top contact type device structure, 1002 is a bottom gate-bottom contact type device structure, 1003 is a top gate-top contact type device structure, and 1004 is a top gate-bottom contact type device structure. 1 represents an organic semiconductor layer, 2 represents a substrate, 3 represents a gate electrode, 4 represents a gate insulating layer, 5 represents a source electrode, and 6 represents a drain electrode.

[0170] Figure 2 One embodiment of the organic transistor of the present invention is shown. Figure 2 The organic transistor 1005 shown corresponds to Figure 1 The bottom gate-bottom contact type 1001 in FIG. 7 represents a pattern, and 8 represents a protective film layer.

[0171] In the organic transistor, there is no particular limitation on the substrate that can be used as long as it can ensure sufficient flatness for manufacturing the element, and examples thereof include: inorganic material substrates such as glass, quartz, alumina, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, etc.; plastics; metals such as gold, copper, chromium, titanium, aluminum, etc.; ceramics; coated paper; surface-coated nonwoven fabrics, etc., and composite materials containing these materials or materials formed by multilayering these materials may also be used. In addition, in order to adjust the surface tension, the surface of these materials may also be coated.

[0172] Examples of plastics used as substrates include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyether sulfone, polyphenylene sulfide, polyphenylene oxide, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, styrene block copolymer, etc. In addition, two or more of the above plastics can be stacked and used as a substrate.

[0173] There is no limitation on the organic semiconductor that can be used in the organic semiconductor layer. Both N-type and P-type organic semiconductors can be used, and it can also be used as a bipolar transistor combining N-type and P-type. In addition, both low-molecular and high-molecular organic semiconductors can be used, and they can also be mixed and used. As specific compounds of organic semiconductors, for example, compounds represented by the following formulas (E-1) to (E-11) can be exemplified.

[0174] [Chemistry 17]

[0175] [Chemistry 18]

[0176] [Chemistry 19]

[0177] [Chemistry 20]

[0178] In the present invention, as a method for forming an organic semiconductor layer, a method of vacuum evaporating an organic semiconductor, or a method of dissolving an organic semiconductor in an organic solvent for coating or printing, etc. can be exemplified, but as long as it is a method that can form a thin film of an organic semiconductor layer, there is no limitation. The concentration of the solution in the case of coating or printing with a solution obtained by dissolving an organic semiconductor layer in an organic solvent varies depending on the structure of the organic semiconductor and the solvent used, and is preferably 0.5% to 5wt% from the viewpoint of more uniformly forming the semiconductor layer and reducing the thickness of the layer. The organic solvent at this time is not limited as long as it is dissolved at a certain concentration in which the organic semiconductor can be formed into a film, and examples thereof include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ -Butyrolactone, 1,3-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, tetradecahydrophenanthrene, 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, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, limonene, etc. In order to obtain a crystalline film with preferred properties, it is suitable to use a solvent with high solubility for dissolving organic semiconductors and a boiling point of 100° C. or above, preferably xylene, cumene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, decahydro-2-naphthol. In addition, a mixed solvent obtained by mixing two or more of the above solvents in an appropriate ratio can also be used.

[0179] In the organic semiconductor layer, various organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added in the form of solid or dispersion in which nanoparticles are dispersed in water or an organic solvent as required, and the polymer solution can be applied on the above-mentioned insulating layer to form a protective film. Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied on the protective film as required.

[0180] As the gate, source or drain that can be used in the present invention, aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, platinum, titanium, tantalum, graphene, carbon nanotubes and other inorganic electrodes, or doped conductive polymers (such as PEDOT-PSS) and other organic electrodes and other conductive materials are exemplified, and these conductive materials can also be used in a plurality of layers. In addition, in order to improve the injection efficiency of carriers, these electrodes can also be surface treated using a surface treatment agent. As such a surface treatment agent, for example, benzenethiol, pentafluorobenzenethiol, etc. can be cited.

[0181] In addition, there is no particular limitation on the method for forming an electrode on the above-mentioned substrate, insulating layer or organic semiconductor layer, and examples include vapor deposition, high-frequency sputtering, electron beam sputtering, and the like. It is also possible to use an ink obtained by dissolving nanoparticles of the above-mentioned conductive material in water or an organic solvent, and perform solution spin coating, drop coating, dip coating, blade coating, mold coating, pad printing, roller coating, gravure printing, flexographic printing, super flexographic printing, screen printing, inkjet printing, letterpress reverse printing, and the like.

[0182] The resin of the present invention can be suitably used for patterns and protective film layers in organic transistors.

[0183] From the viewpoint of the practicality of the organic transistor element, the mobility of the organic transistor according to one embodiment of the present invention is preferably 0.20 cm 2 / Vs or above.

[0184] From the viewpoint of practicality of the organic transistor element, the on-current / off-current ratio of the organic transistor according to one embodiment of the present invention is preferably 10 5 above.

[0185] From the viewpoint of practicality of an organic transistor element, the organic transistor according to one embodiment of the present invention preferably has no hysteresis in source-drain current.

[0186] <Conclusion> It can be seen from the above description that the present invention has the following technical solutions.

[0187] [1] A resin comprising: a repeating unit represented by the following formula (1) containing a photo-crosslinkable group; and One or more units selected from the group consisting of a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group.

[0188] [Chemistry 21]

[0189] In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, A represents an m-valent linking group, R2, R3, R4, R5 and R6 are the same or different and represent one 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 greater than 3, and n represents an integer of m-1.

[0190] [2] The resin according to [1], wherein the resin contains a repeating unit containing a functional group selected from a carboxyl group, a sulfonic group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group and a cyano group as at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group.

[0191] [3] The resin according to [1] or [2], wherein the resin contains a repeating unit represented by the following formula (a) as at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group.

[0192] [Chemistry 22]

[0193] In formula (3), R9 represents a hydrogen atom or a methyl group, and L3 represents a single bond or a divalent linking group.

[0194] [4] The resin according to any one of [1] to [3], wherein the resin contains a repeating unit represented by the following formula (2) as the repeating unit containing a fluorine atom.

[0195] [Chemistry 23]

[0196] In formula (2), R7 represents a hydrogen atom or a methyl group, L2 represents a single bond or a divalent linking group, and Rf1 represents one selected from 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.

[0197] [5] The resin according to any one of [1] to [4], wherein in the above formula (1), A is a linking group selected from the following formulas (a-1) to (a-4).

[0198] [Chemistry 24]

[0199] In formulas (a-1) to (a-4), In the above formula (1), the bonding position with L1 is represented by the front end of the carbon atom. It represents the bonding position to the oxygen atom constituting the ester group in the above formula (1).

[0200] [6] The resin according to [5], wherein in the above formula (1), A is a linking group of the above formula (a-1).

[0201] [7] The resin according to any one of [1] to [6], wherein the resin is soluble in an alkali solution.

[0202] [8] A composition comprising the resin according to any one of [1] to [7] and at least one solvent selected from an organic solvent and a fluorine-based solvent.

[0203] [9] A photocrosslinked product, which is a photocrosslinked product of the resin according to any one of [1] to [7] or the composition according to [8].

[0204]

[10] A pattern consisting of the photo-crosslinked material described in [9].

[0205]

[11] An electronic device comprising the photocrosslinked product described in [9].

[0206] Example Hereinafter, the present invention will be further described in detail by way of examples, but the present invention is not limited to these examples.

[0207] In the examples, the following conditions and apparatuses are used.

[0208] <Monomer purity> Gas chromatography apparatus: manufactured by Shimadzu Corporation, (trade name) GC2014 Column: manufactured by RESTEK Corporation, (trade name) Rxi-1HT, 30 m Using the above gas chromatography apparatus (GC), the purity of the monomer is analyzed.

[0209] <Composition of resin> Using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL Ltd., trade name JNM-ECZ400S), proton nuclear magnetic resonance spectroscopy ( 1 1H-NMR) spectrum analysis is used to obtain the result.

[0210] <Spin coating> MS-A 100 manufactured by Mikasa Co., Ltd. is used.

[0211] <Film thickness measurement> Measurement is performed using a DektakXT Stylus Profiler manufactured by Bruker Corporation.

[0212] <UV irradiation> Using a UV mask aligner, UPE-1605MA, manufactured by Ushio Lighting Co., Ltd., under the condition of a UV intensity of 14.2 mW / cm 2 , the UV irradiation time is adjusted by changing the conveyance speed.

[0213] <Laser microscope> Using a laser microscope, OPTELICS HYBRID, manufactured by Lasertec Corporation, the inkjet-printed organic semiconductor layer or pattern is confirmed.

[0214] In the examples, the following results are obtained.

[0215] Synthesis Example 1 (Synthesis of Photo-crosslinkable Monomer 1) Under a nitrogen atmosphere, add 24 g of glycerol monomethacrylate (BLEMMER GLM, NOF), 32 g of triethylamine and 31 g of toluene to a 500 mL flask and mix thoroughly. In addition, under a nitrogen atmosphere, add 72 g of cinnamoyl chloride and 172 g of toluene to a glass bottle and dissolve them. Then, nitrogen gas is flowed into the flask containing glycerol monomethacrylate, triethylamine and tetrahydrofuran, and the solution dissolved in cinnamoyl chloride is added dropwise using a dropping funnel and stirred for 4 hours. Then, the salt as a by-product is filtered out, and the toluene is removed by an aspirator and vacuum drying. Then, the product is dissolved in 70 g of ethanol to recrystallize it, and the precipitated powder is then vacuum dried. As a result, it was confirmed that the above-mentioned precipitated powder is the substance represented by the following formula (5) (photo-crosslinkable monomer 1). (GC purity 96%) (Photo-crosslinkable monomer 1) [Chemistry 25]

[0216] Example 1 (Polymerization of Resin 1) In a 75 mL glass ampoule, add 1.44 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.4 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 2.23 g of methacrylic acid, 0.25 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.15 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.8 g of 2-butanone, repeat nitrogen substitution and pressure release, and then seal under reduced pressure. The ampoule is placed in a constant temperature bath at 45°C and kept for 24 hours to perform free radical polymerization. After the polymerization reaction is completed, the polymer solution is taken out from the ampoule, and the polymer solution is added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying is performed at 40°C for 8 hours to obtain 4.5 g of resin 1 (yield: about 91%). Through the resin 1 1 H-NMR measurement confirmed that its composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 11 / 8 / 81 (mol %), which was a copolymer represented by formula (6).

[0217] (Resin 1) [Chemistry 26]

[0218] Example 2 (Polymerization of Resin 2) In a 75 mL glass ampoule, add 1.17 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 2.29 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 1.60 g of methacrylic acid, 0.21 g of PERHEXYLND (manufactured by NOF Corporation) as a polymerization initiator, 0.16 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.8 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a thermostatic bath at 45°C for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying was performed at 40°C for 8 hours to obtain 4.6 g of resin 2 (yield: about 91%). Through the resin 2 1 H-NMR measurement confirmed that its composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 11 / 18 / 71 (mol %), and it was a copolymer represented by formula (7).

[0219] (Resin 2) [Chemistry 27]

[0220] Example 3 (Polymerization of Resin 3) In a 75 mL glass ampoule, add 1.61 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 2.1 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 1.62 g of methacrylic acid, 0.19 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.12 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.9 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a thermostatic bath at 45°C for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying was performed at 40°C for 8 hours to obtain 4.26 g of resin 3 (yield: about 85%). Through the resin 3 1H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 15 / 20 / 65 (mol %), which was a copolymer represented by formula (8).

[0221] (Resin 3) [Chemistry 28]

[0222] Example 4 (Polymerization of Resin 4) In a 75 mL glass ampoule, add 1.99 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.95 g of 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 1.16 g of methacrylic acid, 0.18 g of PERHEXYLND (manufactured by NOF Corporation) as a polymerization initiator, 0.11 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.9 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C and kept for 24 hours to perform free radical polymerization. After the polymerization reaction was completed, the polymer solution was taken out from the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, it was vacuum dried at 40°C for 8 hours to obtain 4.57 g of resin 4 (yield: about 91%). Through the resin 4 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 21 / 18 / 61 (mol %), which was a copolymer represented by formula (9).

[0223] (Resin 4) [Chemistry 29]

[0224] Example 5 (Polymerization of Resin 5) In a 75 mL glass ampoule, add 2.19 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.64 g of 1H,1H,2H,2H-nonafluorohexyl methacrylate, 1.28 g of methacrylic acid, 0.19 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.12 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.9 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a thermostatic bath at 45°C and kept for 24 hours to perform free radical polymerization. After the polymerization reaction was completed, the polymer solution was taken out from the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying was performed at 40°C for 8 hours to obtain 4.6 g of resin 5 (yield: about 91%). Through the resin 5 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-nonafluorohexyl methacrylate (fluorinated unit 2) [C-14] / methacrylic acid (acidic functional group unit 1) [D-1] = 22 / 17 / 61 (mol %), and it was a copolymer represented by formula (10).

[0225] (Resin 5) [Chemistry 30]

[0226] Example 6 (Polymerization of Resin 6) In a 75 mL glass ampoule, add 2.12 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.66 g of 1H,1H,2H,2H-nonafluorohexyl methacrylate, 1.28 g of methacrylic acid, 0.19 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.06 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.8 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a thermostatic bath at 45°C for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying was performed at 40°C for 8 hours to obtain 4.2 g of resin 6 (yield: about 84%). Through the resin 6 1H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / 1H,1H,2H,2H-nonafluorohexyl methacrylate (fluorinated unit 2) [C-14] / methacrylic acid (acidic functional group unit 1) [D-1] = 28 / 21 / 51 (mol %), and it was a copolymer represented by formula (11).

[0227] (Resin 6) [Chemistry 31]

[0228] Example 7 (Polymerization of Resin 7) In a 75 mL glass ampoule, add 2.56 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 2.62 g of mono-2-(methacryloyloxy)ethyl phthalate, 0.29 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.35 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 12.1 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a thermostatic bath at 45°C for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, vacuum drying was performed at 40°C for 8 hours to obtain 4.8 g of resin 7 (yield: about 96%). Through the resin 7 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / mono-2-(methacryloyloxy)ethyl phthalate (acidic functional group unit 2) [D-22] = 52 / 48 (mol %), and it was a copolymer represented by formula (12).

[0229] (Resin 7) [Chemistry 32]

[0230] Example 8 (Polymerization of Resin 8) In a 75 mL glass ampoule, add 4.12 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.00 g of methacrylic acid, 0.41 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.62 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 11.9 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the ampoule under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C and kept for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, it was vacuum dried at 40°C for 8 hours to obtain 4.2 g of resin 8 (yield: about 84%). Through the resin 8 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / methacrylic acid (acidic functional group unit 1) [D-1] = 40 / 60 (mol %), and it was a copolymer represented by formula (13).

[0231] (Resin 8) [Chemistry 33]

[0232] Example 9 (Polymerization of Resin 9) In a 75 mL glass ampoule, 3.07 g of the photocrosslinkable monomer 1 obtained in Synthesis Example 1, 2.29 g of mono(2-acryloyloxyethyl) succinate, 0.33 g of PERHEXYL ND (manufactured by NOF Corporation) as a polymerization initiator, 0.40 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 12.5 g of 2-butanone were added, and after repeated nitrogen substitution and pressure release, the ampoule was sealed under reduced pressure. The ampoule was placed in a constant temperature bath at 45°C and kept for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction was completed, the polymer solution was taken out of the ampoule, and the polymer solution was added dropwise to 300 mL of a 1:1 mixed solvent of toluene and hexane to precipitate it, and then washed twice with 150 mL of hexane. Furthermore, it was vacuum dried at 40°C for 8 hours to obtain 3 g of resin 9 (yield: about 60%). Through the resin 9 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / mono(2-acryloyloxyethyl) succinate (acidic functional group unit 3) [D-21] = 54 / 46 (mol %), and it was a copolymer represented by formula (14).

[0233] (Resin 9) [Chemistry 34]

[0234] Example 10 (mixing of resin 6 and resin 7) The resin 6 and the resin 7 obtained as described above were mixed at a ratio of 2:20 (wt %) to obtain a resin mixture.

[0235] Example 11 (mixing of resin 6 and resin 9) The resin 6 and the resin 9 obtained as described above were mixed at a ratio of 2:20 (wt %) to obtain a resin mixture.

[0236] Comparative Example 1 (Polymerization of Resin A) In a 75 mL glass ampoule, add 3.82 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 NOF Corporation) as a polymerization initiator, 0.05 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 12 g of 2-butanone, and after repeated nitrogen substitution and pressure release, seal the mixture under reduced pressure. The ampoule is placed in a constant temperature bath at 45°C and maintained for 24 hours to allow free radical polymerization to proceed. After the polymerization reaction is completed, the polymer solution is taken out of the ampoule, and the polymer solution is added dropwise to 300 mL of methanol to precipitate it, and then washed twice with 150 mL of methanol. Furthermore, vacuum drying is performed at 30°C for 8 hours to obtain 4 g of resin A (yield: about 80%). Through the resin A 1 H-NMR measurement confirmed that the composition was photo-crosslinkable monomer 1 (photo-crosslinkable group unit 1) [B-1] / methyl methacrylate (other units) = 40 / 60 (mol %), and it was a copolymer represented by the following formula (15).

[0237] (Resin A) [Chemistry 35]

[0238] <Evaluation of solubility in alkali solution> The synthesized resins 1 to 9 and resin A were added to each of the following fluorine-based solvents (solvent 1) in a 1 wt % concentration, mixed at room temperature, stirred for 1 hour, and visually confirmed whether they were dissolved. The results are shown in Table 1. In Table 1, the presence of insoluble components or insoluble components is indicated as "insoluble", and the absence of insoluble components or insoluble components is indicated as "soluble".

[0239] Solvent 1: Tetramethylammonium hydroxide aqueous solution (2.38%) It was confirmed that resins 1 to 9 were dissolved in the alkaline solution.

[0240] [Table 1]

[0241] <Evaluation of liquid repellency (water repellency and oil repellency)> 30×30mm after cleaning and drying 2 On a glass (EagleXG manufactured by Corning), a solution of resin 1 or 2 (3 wt%, solvent: N, N-dimethylformamide), a solution of resins 3 to 6 or resin A (3 wt%, solvent: propylene glycol monomethyl ether acetate), a mixed solution of resin 6 and resin 7, or a mixed solution of resin 6 and resin 9 (resin 6: 2 wt%, resin 7 or resin 9: 20 wt%, solvent: propylene glycol monomethyl ether acetate: 78 wt%) was spin-coated at 500 rpm × 5 seconds and 1500 rpm × 20 seconds. UV irradiation was performed at 2000 mJ / cm 2 Using a contact angle meter (DM-300, manufactured by Kyowa Interface Chemical Co., Ltd.), θ The contact angles of water, diiodomethane, m-xylene and tetralin were measured by the 1:1 / 2 method. The results are shown in Table 2.

[0242] It was confirmed that resins 1 to 6, a mixture of resin 6 and resin 7, and a mixture of resin 6 and resin 9 had excellent liquid repellency. On the other hand, resin A did not show excellent liquid repellency.

[0243] [Table 2]

[0244] <Evaluation of curability (crosslinking) and pattern formation> In order to evaluate the curability, resins 1 to 9, a mixture of resin 6 and resin 7, a mixture of resin 6 and resin 9, and resin A were dissolved in the solvent and sensitizer addition conditions shown in Table 3 to prepare solutions. Then, a spin coater was used to coat the 30×30 mm 2 The film was formed on a glass substrate (Eagle XG manufactured by Corning) at 500 rpm for 5 seconds and 1500 rpm for 20 seconds and then dried thoroughly. 2 ~1000mJ / cm 2 The resin film was photo-crosslinked by UV. The thickness of the film was measured using a DektakXT probe profiler manufactured by Bruker and was set as T0. Next, the glass plate coated with the photo-crosslinked resin film was immersed in a tetramethylammonium hydroxide aqueous solution (2.38%) as a good solvent for the resin for 1 minute, then taken out and dried at 150°C for 10 minutes using a hot plate. The thickness of the film after drying was measured and was set as T1. Using these film thickness measurement values, the residual film rate (R) was calculated using the following formula.

[0245] R=T1 / T0×100(%) The photo-crosslinking (curing) property was evaluated by taking the residual film rate (R) of 95% or more as the crosslinking criterion. It should be noted that the lower the UV irradiation dose, the higher (faster) the photo-crosslinking property is. 2 When R 95% or more was achieved under the following UV irradiation doses, it was judged as "cross-linked".

[0246] For pattern formation evaluation, a mask with a side of 50 μ A mask patterned with chromium is used to form a square with 10 squares arranged vertically and 10 squares arranged horizontally. 2 A mask was placed on the film obtained by spin coating the above solution on a glass substrate, and irradiated with UV irradiation at a residual film rate of 95% or more in the curability evaluation. After irradiation, the uncrosslinked part was washed and removed with a tetramethylammonium hydroxide aqueous solution (2.38%) for 1 minute, and a laser microscope was used to confirm whether 100 10×10 μ m 2 Size: 50×50 μ m 2 Pattern of shapes of sizes.

[0247] Solvent 2: N,N-dimethylformamide Solvent 3: Propylene glycol monomethyl ether acetate Sensitizer 1: 4,4′-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry) Resins 1 to 9, a mixture of resin 6 and resin 7, and a mixture of resin 6 and resin 9: 1000 mJ / cm 2 On the other hand, since resin A is insoluble in tetramethylammonium hydroxide aqueous solution (2.38%), it cannot be evaluated.

[0248] Resins 1 to 9, a mixture of resin 6 and resin 7, and a mixture of resin 6 and resin 9 were patterned and showed excellent patterning properties. On the other hand, since resin A was insoluble in tetramethylammonium hydroxide aqueous solution (2.38%), no pattern could be formed.

[0249] [Table 3]

[0250] Description of Reference Numerals 1 Organic semiconductor layer 2 substrate 3. Gate 4 Gate insulation layer 5 Source 6 Drain 7 Pattern 8 Protective film layer.

Claims

1. A resin, characterized in that contain: a repeating unit represented by the following formula (1) containing a photo-crosslinkable group; and one or more units selected from the group consisting of a repeating unit containing a fluorine atom, a repeating unit containing an acidic functional group, and a repeating unit containing a hydrophilic functional group, ， In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, A represents an m-valent linking group, R2, R3, R4, R5 and R6 are the same or different and represent one selected from the group consisting of a hydrogen atom, a halogen atom, a straight-chain 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 straight-chain 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 greater than 3, and n represents an integer of m-1.

2. The resin according to claim 1, wherein The resin contains a repeating unit containing a functional group selected from a carboxyl group, a sulfonic group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group, and a cyano group as at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group.

3. The resin according to claim 1 or 2, wherein The resin contains a repeating unit represented by the following formula (a) as at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group, ， In formula (3), R9 represents a hydrogen atom or a methyl group, and L3 represents a single bond or a divalent linking group.

4. The resin according to claim 1 or 2, wherein The resin contains a repeating unit represented by the following formula (2) as the repeating unit containing a fluorine atom, ， In formula (2), R7 represents a hydrogen atom or a methyl group; L2 represents a single bond or a divalent linking group; and Rf1 represents a straight-chain 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.

5. The resin according to claim 1 or 2, wherein In the formula (1), A is a linking group selected from the following formulas (a-1) to (a-4), ， In formulas (a-1) to (a-4), represents the bonding position with L1 in the above formula (1), the front end of the carbon atom It represents the bonding position to the oxygen atom constituting the ester group in the above formula (1).

6. The resin according to claim 5, wherein In the formula (1), A is a linking group of the formula (a-1).

7. The resin according to claim 1 or 2, wherein The resin is soluble in alkali solution.

8. A composition, characterized in that The method comprises the resin according to claim 1 and at least one solvent selected from an organic solvent and a fluorine-based solvent.

9. A photo-crosslinked product, characterized in that: It is a photo-crosslinked product of the resin according to claim 1 or 2 or the composition according to claim 8.

10. A pattern, characterized in that: The photo-crosslinked product according to claim 9.

11. An electronic device, characterized in that: A photo-crosslinked product according to claim 9.

Images