Resin, composition, photocrosslinked product, pattern, and electronic device comprising same

Abstract

The purpose of one aspect of the present invention is to provide a resin that has liquid repellency and high solubility in alkaline solution, the resin being rendered insoluble in solvents through photocrosslinking at a low exposure level. A resin according to one aspect of the present invention contains: repeating units expressed by formula (1), said repeating units each including a photocrosslinkable group; and one or more units selected from the group consisting of repeating units that each include a fluorine atom, repeating units that each include an acidic functional group, and repeating units that each include a hydrophilic functional group. (In the formula, R1 represents hydrogen or methyl, L1 represents a single bond or a linking group, A represents a linking group, and R2 to R6 represent one form the group consisting of hydrogen, halogen, alkyl, alkyl halide, alkoxy, aryl, aryloxy, cyano, and amino.)

Description

Resin, composition, photocrosslinked product, pattern, and electronic device including the same

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

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

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

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

[0005] Here, we will explain the manufacturing method of organic electroluminescent devices used in organic electroluminescent displays and organic electroluminescent lighting. First, the polymer material is applied to a substrate, and the desired pattern is formed by photocrosslinking. The unphotocrosslinked portions are then removed. The remaining portions become the pattern. Various functional layers are then laminated on the portions from which the polymer material has been removed (inside the pattern). While a promising technology for forming the functional layers is to use ink-like raw materials, the material that makes up the pattern is expected to have liquid-repellent properties to prevent ink adhesion inside the pattern and ink leakage beyond the portions from which the polymer material has not been removed (outside the pattern). Furthermore, alkaline solutions are often used in the manufacture of organic electroluminescent devices, and solubility in alkaline solutions is required.

[0006] As such a material, Patent Document 1 lists a negative photosensitive resin composition that is highly photoreactive, can be patterned with an alkaline solution, and can form a liquid-repellent coating, as well as a photocured pattern produced from the composition. However, because the resin in this composition is not photocurable, it must be thermally cured at high temperatures for a long period of time after patterning. Long-term treatment at high temperatures can cause a decrease in the performance of electronic devices and limit the selection of plastic substrates. Therefore, there was a need for the development of a photocrosslinkable fluorine-based material to prevent the decrease in performance of electronic devices.

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

[0008] Examples of photocrosslinkable resins include resins such as those disclosed in Non-Patent Document 2, which use anthracene crosslinking groups.

[0009] Japanese Patent No. 5932512 Japanese Patent No. 6281427

[0010] Appl. Phys. Express 7, 101602 (2014) J Polym Sci A Polym Chem 53, 1252 (2015)

[0011] However, the resin described in Non-Patent Document 2 has low photocrosslinkability and requires a high exposure dose. It also lacks solubility in alkaline solutions. Therefore, there is a demand for a resin that has high photoreactivity and is soluble in alkaline solutions.

[0012] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a resin that has liquid-repellent properties, is soluble in alkaline solutions, and can be made insoluble in solvents by photocrosslinking with a low exposure dose.

[0013] As a result of extensive research into solving the above problems, the present inventors have found that a resin having a specific structure can solve the above problems, and have thus completed the present invention.

[0014] That is, the resin according to one aspect of the present invention contains a repeating unit represented by the following formula (1) 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:

[0015]

[0016] (In formula (1), R １ represents a hydrogen atom or a methyl group, L １ represents a single bond or a divalent linking group, A represents an m-valent linking group, R ２ , R ３ , R ４ , R ５ and R ６ are the same or different and represent one member selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group; m represents an integer of 3 or more, and n represents an integer equal to m-1.

[0017] According to the present invention, a resin is obtained that has liquid repellency, is soluble in an alkaline solution, and is insoluble in a solvent when photocrosslinked with a low exposure dose. The resin can be used for pattern formation, and by forming a pattern using the resin, deterioration in the performance of the resulting electronic device can be prevented.

[0018] 1 is a diagram showing a cross-sectional shape of an organic transistor, which is one embodiment of an electronic device of the present invention.

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

[0020] The resin of the present invention is a resin containing a 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]

[0022] The resin of the present invention has a photocrosslinkable group, which allows the resin to exhibit high photoreactivity and selectively insolubilize only the light-irradiated portions of a film obtained by applying the resin.

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

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

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

[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 a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-tetrahydrodicyclopentadiene-diyl group, and among these, a cyclohexylene group is preferable.

[0029] Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and among these, a phenylene group is preferred.

[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 preferable, and (—C(═O)O—) is even more preferable.

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

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

[0033] A may be an m-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, since this improves the solubility of the resulting resin in organic solvents and fluorine-containing solvents.

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

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

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

[0038] Among these, the m-valent hydrocarbon group A is preferably one type of linking group selected from the group consisting of the following formulae (a-1) to (a-4):

[0039]

[0040] In formulas (a-1) to (a-4), *L represents L in formula (1). １ The * before the carbon atom indicates the bonding position with the oxygen atom constituting the ester group in formula (1).

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

[0042] In formula (1), R ２ , R ３ , R ４ , R ５ and R ６ may be the same or different and represent one member selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group.

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

[0044] As 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, and among these, a methyl group or an ethyl group is preferred.

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

[0046] As the cyclic alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms is preferred. Specific examples include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and among these, a cyclohexyl group is preferred.

[0047] As the linear halogenated alkyl group having 1 to 20 carbon atoms, a linear fluoroalkyl group having 1 to 4 carbon atoms is preferred. Specific examples include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group, and among these, a trifluoromethyl group is preferred.

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

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

[0050] As the aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 12 carbon atoms is preferred. Specific examples include a phenyloxy group and a 2-naphthyloxy group, and among these, a phenyloxy group is preferred.

[0051] The amino group may be, for example, a primary amino group (—NH ２ ), secondary amino groups such as a methylamino group; and tertiary amino groups such as a dimethylamino group, a diethylamino group, a dibenzylamino group, and groups in which the nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, piperazine, etc.) serves as a bonding bond.

[0052] R ２ , R ３ , R ４ , R ５ and R ６ are each preferably independently one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom, and a linear halogenated alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, in order to further increase the solubility in fluorine-based solvents, photocurability, and liquid repellency of the resin.

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

[0054]

[0055]

[0056]

[0057]

[0058]

[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, which facilitates layer separation in a film obtained by coating a composition containing the resin.

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

[0062]

[0063] In formula (2), R ７ represents a hydrogen atom or a methyl group.

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

[0065] L ２The divalent linking group in is preferably a divalent linking group combining at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (—O—), a carbonyl group (—C(═O)—), and an imino group (—NH—). This allows for the formation of a flat, crack-free film.

[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 a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-tetrahydrodicyclopentadiene-diyl group, and among these, a cyclohexylene group is preferable.

[0069] Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and among these, a phenylene group is preferred.

[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 preferable, and (—C(═O)O—) is even more preferable.

[0071] In formula (2), Rf １represents one of the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.

[0072] Rf １ is a fluoroalkyl group, the resin according to one aspect of the present invention exhibits affinity with fluorine-based solvents and liquid repellency.

[0073] Rf １ When Rf is a linear fluoroalkyl group, the specific １ Examples of L include 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, each of which is substituted with a fluorine atom. ２ Rf in １ When the bonding element to Rf is oxygen, １ The substitution position of the fluorine atom in ２ It may be on a carbon atom other than the carbon atom directly bonded to oxygen.

[0074] Rf １ When Rf is a linear fluoroalkyl group, １ is preferably a group represented by the following formula (3):

[0075]

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

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

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

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

[0080] Rf １ When is a group represented by formula (3), the synthesis of a monomer that serves as a raw material for the repeating unit represented by formula (2) becomes easier.

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

[0082] Rf １ When Rf is a cyclic fluoroalkyl group, specific Rf １ Examples of such groups include a 1,2,2,3,3,4,4,5,5-nonafluorocyclopentane group and a 1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexane group.

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

[0084]

[0085] In formula (4), R ８ 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 to 4, preferably 1 or 2.

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

[0089] The resin according to one embodiment of the present invention may contain one type of repeating unit represented by the formula (2), or may contain two or more types of repeating units. １ a repeating unit having a linear fluoroalkyl group as described above, and Rf １The resin according to one aspect of the present invention may contain both repeating units having the branched fluoroalkyl group described above, or may contain two or more repeating units having linear fluoroalkyl groups with different carbon numbers. The resin according to one aspect of the present invention preferably contains one repeating unit represented by 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 type selected from the group consisting of repeating units represented by the following formulae (C-1) to (C-33):

[0091]

[0092]

[0093]

[0094] As the repeating unit containing a fluorine atom, one selected from the group consisting of repeating units represented by the formulae (C-1) to (C-33) is preferred, one selected from the group consisting of repeating units represented by the formulae (C-9) to (C-33) is more preferred, and one selected from the group consisting of repeating units represented by the formulae (C-14) to (C-21) or the group consisting of repeating units represented by the formulae (C-27) to (C-33) is particularly preferred.

[0095] 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, from the viewpoint of exhibiting solubility in an alkaline solution.

[0096] Specifically, it is preferable that at least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group contains a repeating unit containing a functional group selected from a carboxyl group, a sulfo group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group, and a cyano group, and it is more preferable that the repeating unit contains a carboxyl group.

[0097] At least one of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group may be used alone, or two or more of them may be used in combination.In addition, when the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group have the same chemical structural formula, they are counted as one type.In addition, the repeating unit used may be a repeating unit containing an acidic and hydrophilic functional group, or a repeating unit containing both an acidic and non-hydrophilic functional group and a hydrophilic and non-acidic functional group.

[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]

[0100] (In formula (a), R ９ represents a hydrogen atom or a methyl group. ３ represents a single bond or a divalent linking group.

[0101] L ３ The divalent linking group in is preferably a divalent linking group combining at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (—O—), a carbonyl group (—C(═O)—), and an imino group (—NH—). This makes it possible to form a flat, crack-free film.

[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 a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-tetrahydrodicyclopentadiene-diyl group, and among these, a cyclohexylene group is preferable.

[0105] Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and among these, a phenylene group is preferred.

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

[0107] L ３ is more preferably a single bond or an arylene group having 6 to 12 carbon atoms, and even more preferably a single bond or a phenylene group.

[0108]

[0047] Specific examples of the repeating unit containing an acidic functional group and the repeating unit containing a hydrophilic functional group in the resin related to one aspect of the present invention include one type selected from the group consisting of repeating units represented by the following formulas (D-1) to (D-23). ​​Among these, (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 even more preferred.

[0109] In the following formula, R ９ is a hydrogen atom or a methyl group.

[0110]

[0111] From the viewpoint of increasing the solubility in an alkaline solution and enabling more efficient photocuring, the resin according to one aspect of the present invention preferably contains 5 mol % or more and 50 mol % or less of the repeating unit represented by formula (1), and more preferably 5 mol % or more and 40 mol % or less.

[0112] Furthermore, the resin according to one aspect of the present invention preferably contains 5 mol % to 50 mol %, more preferably 5 mol % to 40 mol %, and even more preferably 5 mol % to 30 mol % of repeating units containing fluorine atoms.

[0113] Furthermore, the resin according to one embodiment of the present invention preferably contains 20 mol % or more and 90 mol % or less of repeating units containing an acidic functional group, more preferably 30 mol % or more and 90 mol % or less, and even more preferably 30 mol % or more and 80 mol % or less.

[0114] Furthermore, the resin according to one aspect of the present invention preferably contains 20 mol % or more and 90 mol % or less of repeating units containing hydrophilic functional groups, more preferably 30 mol % or more and 90 mol % or less, and even more preferably 30 mol % or more and 80 mol % or less.

[0115] The resin according to one embodiment of the present invention may contain other monomer repeating units as long as the repeating units do not deviate from the object of the present invention. Examples of other monomer repeating units include olefin residue units such as an ethylene residue unit, a propylene residue unit, and a 1-butene residue unit; vinyl aromatic hydrocarbon residue units such as a styrene residue unit and an α-methylstyrene residue unit; vinyl carboxylate ester residue units such as a vinyl acetate residue unit, a vinyl propionate residue unit, and a vinyl pivalate residue unit; vinyl ether residue units such as a methyl vinyl ether residue unit, an ethyl vinyl ether residue unit, and a butyl vinyl ether residue unit; N-substituted maleimide residue units such as an N-methylmaleimide residue unit, an N-cyclohexylmaleimide residue unit, and an N-phenylmaleimide residue unit; an acrylonitrile residue unit; a methacrylonitrile residue unit; and a silicone residue unit.

[0116] The molecular weight of the resin of the present invention is not limited, and may be, for example, 2,000 to 10,000,000 (g / mol). From the viewpoint of the solution viscosity and mechanical strength of the resulting resin, the molecular weight is preferably 10,000 to 1,000,000 (g / mol).

[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 a monomer that forms a repeating unit represented by formula (1), a monomer that forms a repeating unit containing a fluorine atom as described above, a monomer that forms a repeating unit containing an acidic functional group, a monomer that forms a repeating unit containing a hydrophilic functional group, and a monomer that forms any other repeating unit, and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

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

[0119] The alkaline solution will be described below.

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

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

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

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

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

[0125] Examples of alcohol amines include dimethylethanolamine and triethanolamine.

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

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

[0128] Among these, inorganic alkalis, tertiary amines, alcohol amines, quaternary ammonium salts, etc. are preferred as alkaline solutions, with quaternary ammonium salts being particularly preferred.

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

[0130] The composition according to one embodiment of the present invention will be described below.

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

[0132] The fluorine-based solvent may be any solvent capable of dissolving the resin of the present invention. By using a fluorine-based solvent as a solvent for dissolving the resin, damage to device components mainly composed of organic substances can be minimized during the fabrication of electronic devices by an all-printing method, allowing the electronic devices to fully exhibit their performance.

[0133] The fluorine atom content of the fluorine-based compound constituting the fluorine-based solvent is 50% by mass or more and 70% by mass or less, more preferably 55% by mass or more and 70% by mass or less, based on the total mass of the fluorine-based compound. If it exceeds 70% by mass, the resin may not be sufficiently dissolved. If it is less than 50% by mass, the surface of the organic semiconductor film may be dissolved or swelled when the solvent is applied or printed on the organic semiconductor film.

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

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

[0136] Specific examples of such fluorine-containing hydrocarbons include butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, and benzene in which at least one hydrogen atom has been substituted with a fluorine atom. Specific examples include fluorine-containing hydrocarbons such as 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 2H,3H-decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, hexafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, and hexafluorobenzene.

[0137] The boiling point of the fluorine-containing hydrocarbon is preferably not more than 200° C., more preferably not more than 180° C. When the boiling point of the fluorine-containing hydrocarbon is not more than 200° C., the fluorine-containing hydrocarbon can be easily evaporated and removed by heating.

[0138] Among the above-mentioned fluorine-containing hydrocarbons, the following can be given as examples having particularly preferable 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] Furthermore, because of its low ozone depletion potential, a fluorine-containing ether can be used as the fluorine-based solvent. In particular, the boiling point of the fluorine-containing ether is preferably 200° C. or lower, more preferably 180° C. or lower. When the boiling point of the fluorine-containing ether is 200° C. or lower, the fluorine-containing ether can be easily evaporated and removed from the 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, and ethyl nonafluorobutyl ether.

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

[0143] A fluorine-containing alcohol can be used as the fluorine-based solvent. The fluorine-containing alcohol used preferably has a boiling point of 200° C. or lower, more preferably 180° C. or lower. When the boiling point of the fluorine-containing alcohol is 200° C. or lower, the fluorine-containing alcohol can be easily evaporated and removed by heating.

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

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

[0146] The organic solvent used in the composition of the present invention refers to an organic solvent that does not fall under the category of a fluorine-containing solvent. There is no limitation on the organic solvent as long as it dissolves 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, 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-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-Methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,Examples include 1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a film with desirable properties, an organic solvent with high resin dissolving power is suitable, and xylene and propylene glycol monomethyl ether acetate are preferred. Mixed solvents containing two or more of the aforementioned solvents in appropriate ratios can also be used.

[0147] A composition of a resin and at least one of an organic solvent and a fluorine-containing solvent 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] The composition according to one aspect of the present invention may also contain a photosensitizer. The photosensitizer may be any agent that accelerates the crosslinking reaction of the photocrosslinkable group.

[0149] Examples of photosensitizers include acyloins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; carbonyls such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzil; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, and tetramethylthiuram disulfide; phenones such as acetophenone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methoxybenzophenone, and 2,4,6-trimethoxybenzophenone; p-toluenesulfonyl chloride, and 1-naphthalene. Examples of suitable photosensitizers include sulfonyl halides such as sulfonyl chloride, 1,3-benzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, and p-acetamidobenzenesulfonyl chloride; aromatic nitro compounds such as 5-nitrofluorene, 5-nitroacenaphthene, N-acetyl-4-nitro-1-naphthylamine, and biclamide; coumarins such as 7-diethylamino-3-thenoylcoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, bisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; and dyes such as ethionine, thionine, and methylene blue. The addition of a photosensitizer enables crosslinking (insolubilization) of the resin according to one embodiment of the present invention at a lower exposure dose. Furthermore, two or more types of such sensitizers can be used in combination as needed.

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

[0151] A pattern according to one embodiment of the present invention will be described below.

[0152] A pattern can be formed using the resin of the present invention. More specifically, a photocrosslinked product is obtained using the resin of the present invention or a composition thereof, and a pattern is formed. 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 aspect of the present invention.

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

[0154] Examples of methods for forming the coating film include spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, gravure printing, flexographic printing, superflexographic printing, screen printing, inkjet printing, letterpress reverse printing, reverse offset printing, and adhesion contrast printing.

[0155] Next, the coating film is dried. By drying, the solvent volatilizes, and a non-tacky coating film is obtained. Drying conditions vary depending on the boiling point and blending ratio of the solvent used, but can be used in a wide range of conditions, preferably 50 to 150°C, for 10 to 2000 seconds.

[0156] When a coating film having a predetermined shape, i.e., the same shape as a desired pattern, is formed using a printing method during coating film formation, exposure to light causes the coating film having the predetermined shape to be photocrosslinked to obtain a photocrosslinked product, which is then fixed, thereby forming a pattern.

[0157] On the other hand, if a coating film having a predetermined shape is not formed during coating film formation, a pattern can be formed from the coating film using photolithography. When using photolithography, the dried coating film is first exposed to light through a mask having a predetermined shape, i.e., a shape that can form the desired pattern, to cause photocrosslinking.

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

[0159] Irradiation with ultraviolet light is usually carried out in the atmosphere, but can also be carried out in an inert gas or under a certain amount of inert gas flow as needed. If necessary, the photo-crosslinking reaction can be promoted by adding the above-mentioned photosensitizer. The unexposed portions are then developed with a developer to remove them. The developer may be any alkaline solution or organic solvent that dissolves the uncured resin, and examples of such a developer include the above-mentioned alkaline solutions; aromatic solvents such as benzene, toluene, and xylene; ether-based solvents such as dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate; 2H,3H-decaf Fluorine-based solvents such as fluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, hexafluorobenzene, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H,7H-dodecafluoro-1-heptanol, and 2,2,3,3,4,4,4-heptafluoro-1-butanol can be used.

[0160] The development time is preferably 30 to 300 seconds. The development method may be either a puddle method or a dipping method. After development, the substrate is washed with a solvent and air-dried with compressed air or compressed nitrogen to remove the solvent from the substrate. Subsequently, a pattern is formed by heat treatment using a heating device such as a hot plate or oven, preferably at 40 to 150°C for 5 to 90 minutes.

[0161] After forming a pixel pattern through the above-mentioned photolithography process, contamination on the substrate surface within the pixels may be removed. For example, the substrate surface may be cleaned by irradiating it with short-wavelength ultraviolet light such as a low-pressure mercury lamp or excimer UV, or by photo-ashing treatment. Photo-ashing treatment is a treatment in which short-wavelength ultraviolet light is irradiated in the presence of ozone gas. The short-wavelength ultraviolet light is light having a main peak at a wavelength of 100 to 300 nm.

[0162] If the liquid repellency is reduced after removing the stains on the substrate surface within the pixels, the liquid repellency may be restored by heat treatment or the like.

[0163] Thus, the resin of the present invention is soluble in an alkaline solution or an organic solvent, and upon irradiation with light, the photocrosslinkable groups in the side chains are crosslinked and hardened, rendering the resin insoluble in the solvent used. Utilizing this property, the resin of the present invention can be used as a negative resist in which, upon crosslinking by irradiation with light, the unexposed portions are removed by an alkaline solution or an organic solvent.

[0164] After patterning using the resin of the present invention, the portion where the resin remains crosslinked (outside the pattern) preferably has a contact angle with the ink of 40° or more, more preferably 50° or more, to prevent the ink from wetting and spreading to form the functional layer.

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

[0166] The resin of the present invention has excellent liquid repellency and can be used as a pattern material when producing organic transistor elements, color filters, and organic EL elements. The resin of the present invention can also be used in electronic devices including the organic transistor elements, color filters, and organic EL elements.

[0167] The electronic device according to one embodiment of the present invention will be described in detail below.

[0168] The resin of the present invention can be used in electronic devices, more specifically, in electronic devices comprising a photo-crosslinked product of a composition containing the resin of the present invention and at least one solvent selected from an organic solvent and a fluorinated solvent, and examples of such electronic devices include organic transistors.

[0169] A typical organic transistor has a gate insulating layer on a substrate, and is obtained by further depositing an organic semiconductor layer on this gate insulating layer, and then providing a source electrode, a drain electrode, and a gate electrode. An example of an organic transistor device structure is shown in a cross-sectional view in FIG. 1. 1001 denotes a bottom gate-top contact type, 1002 a bottom gate-bottom contact type, 1003 a top gate-top contact type, and 1004 a top gate-bottom contact type device structure. 1 denotes an organic semiconductor layer, 2 a substrate, 3 a gate electrode, 4 a gate insulating layer, 5 a source electrode, and 6 a drain electrode.

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

[0171] The substrate that can be used in the organic transistor is not particularly limited as long as it can ensure sufficient flatness for fabricating an element, and examples thereof include inorganic material substrates such as glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; surface-coated nonwoven fabric; and the like. Composite materials made of these materials or multilayer materials of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

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

[0173] There are no limitations on the organic semiconductor that can be used in the organic semiconductor layer; either N-type or P-type organic semiconductors can be used, and a bipolar transistor combining N-type and P-type can also be used. Also, either low-molecular-weight or high-molecular-weight organic semiconductors can be used, and a mixture of these can also be used. Specific examples of organic semiconductor compounds include compounds represented by the following formulas (E-1) to (E-11).

[0174]

[0175]

[0176]

[0177]

[0178] In the present invention, examples of methods for forming an organic semiconductor layer include a method of vacuum vapor deposition of an organic semiconductor, or a method of dissolving an organic semiconductor in an organic solvent and coating or printing the solution, but there are no limitations as long as the method can form a thin film of an organic semiconductor layer. When coating or printing an organic semiconductor layer using a solution obtained by dissolving the organic semiconductor layer in an organic solvent, the concentration of the solution varies depending on the structure of the organic semiconductor and the solvent used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the layer thickness, it is preferably 0.5 wt % to 5 wt %. The organic solvent used in this case is not limited as long as it dissolves the organic semiconductor at a certain concentration that allows film formation, and examples thereof include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a mixture of dimethylnaphthalene isomers, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, 3-methyl-4-phenylpropanol, 1,2,4-trimethylbenzene, 1,4-dimethyl-2,4-phenylpropanol, 1,2,4-trimethylbenzene ... -Methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,Examples include 8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a crystal film with desirable properties, a solvent with a high dissolving power for dissolving organic semiconductors and a boiling point of 100°C or higher is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. Mixed solvents containing two or more of the above-mentioned solvents in appropriate proportions can also be used.

[0179] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles, can be added to the organic semiconductor layer as needed, either as a solid or as a dispersion of nanoparticles in water or an organic solvent, and a protective film can be formed by coating the insulating layer with the polymer solution. Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied to this protective film as needed.

[0180] Examples of the gate electrode, source electrode, or drain electrode that can be used in the present invention include conductive materials such as inorganic electrodes made of aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, platinum, titanium, tantalum, graphene, and carbon nanotubes, and organic electrodes made of doped conductive polymers (e.g., PEDOT-PSS). Multiple layers of these conductive materials can also be stacked and used. Furthermore, to increase the carrier injection efficiency, these electrodes can be surface-treated using a surface treatment agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

[0181] Furthermore, there are no particular limitations on the method for forming an electrode on the substrate, insulating layer, or organic semiconductor layer, and examples thereof include vapor deposition, high-frequency sputtering, and electron beam sputtering. It is also possible to employ methods such as solution spin coating, drop casting, dip coating, doctor blade coating, die coating, pad printing, roll coating, gravure printing, flexographic printing, superflexographic printing, screen printing, inkjet printing, and letterpress reverse printing using an ink in which nanoparticles of the conductive material are dissolved in water or an organic solvent.

[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 practicality of the organic transistor element, the organic transistor according to one aspect of the present invention has a mobility of 0.20 cm ２ It is preferable that the voltage Vs is equal to or higher than / Vs.

[0184] From the viewpoint of practicality of the organic transistor element, the organic transistor according to one aspect of the present invention has an on-current / off-current ratio of 10 ５ It is preferable that this is equal to or greater than this.

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

[0186] <Summary> As can be understood from the above description, the present invention has the following gist.

[0187] [1] A resin containing a repeating unit represented by the following formula (1) 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:

[0188]

[0189] (In formula (1), R １ represents a hydrogen atom or a methyl group, L １ represents a single bond or a divalent linking group, A represents an m-valent linking group, R ２ , R ３ , R ４ , R ５ and R ６ are the same or different and represent one member selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group; m represents an integer of 3 or more, and n represents an integer equal to 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 sulfo 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 the acidic functional group and the repeating unit containing the 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 the acidic functional group and the repeating unit containing the hydrophilic functional group:

[0192]

[0193] (In formula (3), R ９ represents a hydrogen atom or a methyl group.３ 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]

[0196] (In formula (2), R ７ represents a hydrogen atom or a methyl group. ２ represents a single bond or a divalent linking group, Rf １ represents one of the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.

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

[0198]

[0199] (In formulas (a-1) to (a-4), *L represents L in formula (1) １ The * before the carbon atom represents the bonding position with the oxygen atom constituting the ester group in formula (1).

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

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

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

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

[0204]

[10] A pattern composed of the photocrosslinked product according to [9].

[0205]

[11] An electronic device comprising the photocrosslinked product according to [9].

[0206] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0207] In the examples, the following conditions and apparatus were used.

[0208] <Monomer Purity> Gas chromatograph: Shimadzu Corporation, product name GC2014 Column: Restek Corporation, product name Rxi-1HT, 30 m The purity of the monomer was analyzed using the above gas chromatograph (GC).

[0209] <Resin Composition> Proton nuclear magnetic resonance spectroscopy ( １ H-NMR spectral analysis.

[0210] <Spin Coating> MS-A100 manufactured by Mikasa Co., Ltd. was used.

[0211] <Film Thickness Measurement> Measurement was carried out using a DektakXT stylus profiler manufactured by Bruker.

[0212] <UV irradiation> A UV mask aligner UPE-1605MA manufactured by Ushio Lighting Co., Ltd. was used, and the UV intensity was 14.2 mW / cm ２ Under the above conditions, the conveying speed was changed to adjust the UV irradiation time.

[0213] <Laser Microscope> The inkjet-printed organic semiconductor layer or pattern was observed using a laser microscope, OPTELICS HYBRID, manufactured by Lasertec Corporation.

[0214] In the examples, the following results were obtained:

[0215] Synthesis Example 1 (Synthesis of Photocrosslinkable Monomer 1) 24 g of glycerin monomethacrylate (Blenmer GLM, NOF Corp.), 32 g of triethylamine, and 31 g of toluene were placed in a 500 mL flask under a nitrogen atmosphere and thoroughly mixed. Also, 72 g of cinnamic acid chloride and 172 g of toluene were placed in a glass bottle under a nitrogen atmosphere and dissolved. Nitrogen was then purged into the flask containing glycerin monomethacrylate, triethylamine, and tetrahydrofuran, and the cinnamic acid chloride solution was added dropwise using a dropping funnel and stirred for 4 hours. The mixture was then filtered to remove the by-product salt, and the toluene was removed using an aspirator and vacuum drying. The product was then dissolved in 70 g of ethanol and recrystallized, and the precipitated powder was vacuum dried. As a result, the precipitated powder was confirmed to be a substance represented by the following formula (5) (photocrosslinkable monomer 1). (GC purity: 96%)

[0216] (Photocrosslinkable monomer 1)

[0217]

[0218] Example 1 (Polymerization of Resin 1) 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 (NOF Corp.) 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 were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of hexane, followed by two washes with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours afforded 4.5 g of Resin 1 (yield: approximately 91%). Resin 1 １By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 11 / 8 / 81 (mol %), and that it was a copolymer represented by formula (6).

[0219] (Resin 1)

[0220]

[0221] Example 2 (Polymerization of Resin 2) A 75 mL glass ampoule was charged with 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 Perhexyl ND (NOF Corp.) 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. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dripping into 300 mL of hexane. The polymer solution was then washed twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 4.6 g of Resin 2 (yield: approximately 91%). Resin 2 １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 11 / 18 / 71 (mol %), and that it was a copolymer represented by formula (7).

[0222] (Resin 2)

[0223]

[0224] Example 3 (Polymerization of Resin 3) A 75 mL glass ampoule was charged with 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 (NOF Corp.) 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. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of hexane, followed by two washes with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 4.26 g of Resin 3 (yield: approximately 85%). Resin 3 １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 15 / 20 / 65 (mol %), and that it was a copolymer represented by formula (8).

[0225] (Resin 3)

[0226]

[0227] Example 4 (Polymerization of Resin 4) A 75 mL glass ampoule was charged with 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 Perhexyl ND (NOF Corp.) 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. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of hexane, followed by two washes with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 4.57 g of Resin 4 (yield: approximately 91%). Resin 4 １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate (fluorine-based unit 1) [C-16] / methacrylic acid (acidic functional group unit 1) [D-1] = 21 / 18 / 61 (mol %), and that it was a copolymer represented by formula (9).

[0228] (Resin 4)

[0229]

[0230] Example 5 (Polymerization of Resin 5) 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 (NOF Corp.) 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 were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of hexane. The polymer solution was then washed twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours afforded 4.6 g of Resin 5 (yield: approximately 91%). Resin 5 １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-nonafluorohexyl methacrylate (fluorine-based unit 2) [C-14] / methacrylic acid (acidic functional group unit 1) [D-1] = 22 / 17 / 61 (mol %), and that it was a copolymer represented by formula (10).

[0231] (Resin 5)

[0232]

[0233] Example 6 (Polymerization of Resin 6) 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 (NOF Corp.) 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 were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of hexane. The polymer solution was then washed twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours afforded 4.2 g of Resin 6 (yield: approximately 84%). Resin 6 １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / 1H,1H,2H,2H-nonafluorohexyl methacrylic acid (fluorine-based unit 2) [C-14] / methacrylic acid (acidic functional group unit 1) [D-1] = 28 / 21 / 51 (mol %), and that it was a copolymer represented by formula (11).

[0234] (Resin 6)

[0235] Example 7 (Polymerization of Resin 7) 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 (NOF Corp.) 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 were placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropping it into 300 mL of hexane. The polymer solution was then washed twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 4.8 g of Resin 7 (yield: approximately 96%). １By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / mono-2-(methacryloyloxy)ethyl phthalate (acidic functional group unit 2) [D-22]=52 / 48 (mol %), and that it was a copolymer represented by formula (12).

[0236] (Resin 7)

[0237]

[0238] Example 8 (Polymerization of Resin 8) 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 (NOF Corp.) 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 were placed in a 75 mL glass ampoule, and after repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropping it into 300 mL of hexane, followed by washing twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 4.2 g of Resin 8 (yield: approximately 84%). １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / methacrylic acid (acidic functional group unit 1) [D-1]=40 / 60 (mol %), and that it was a copolymer represented by formula (13).

[0239] (Resin 8)

[0240]

[0241] Example 9 (Polymerization of Resin 9) 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 (NOF Corp.) 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 placed in a 75 mL glass ampoule. After repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and maintained for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropwise addition to 300 mL of a 1:1 mixed solvent of toluene and hexane. The polymer solution was then washed twice with 150 mL of hexane. The resulting mixture was further vacuum dried at 40°C for 8 hours to obtain 3 g of Resin 9 (yield: approximately 60%). １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / mono(2-acryloyloxyethyl) succinate (acidic functional group unit 3) [D-21]=54 / 46 (mol %), and that it was a copolymer represented by formula (14).

[0242] (Resin 9)

[0243]

[0244] Example 10 (Mixture of Resin 6 and Resin 7) Resin 6 and resin 7 obtained as described above were mixed in a ratio of 2:20 (wt %) to obtain a resin mixture.

[0245] Example 11 (Mixing Resin 6 and Resin 9) Resin 6 and Resin 9 obtained as described above were mixed in a ratio of 2:20 (wt %) to obtain a resin mixture.

[0246] Comparative Example 1 (Polymerization of Resin A) 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 Corp.) 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 were placed in a 75 mL glass ampoule, and after repeated nitrogen substitution and depressurization, the ampoule was sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After completion of the polymerization reaction, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropping it into 300 mL of methanol, followed by washing twice with 150 mL of methanol. Further vacuum drying at 30°C for 8 hours yielded 4 g of Resin A (yield: approximately 80%). １ By H-NMR measurement, it was confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking group unit 1) [B-1] / methyl methacrylate (other units) = 40 / 60 (mol %), and that it was a copolymer represented by the following formula (15).

[0247] (Resin A)

[0248]

[0249] <Evaluation of Solubility in Alkaline Solution> The synthesized Resins 1 to 9 and Resin A were added to each of the following fluorine-based solvents (Solvent 1) so as to give a concentration of 1 wt %, mixed at room temperature, and stirred for 1 hour, after which dissolution was confirmed visually. The results are shown in Table 1. In Table 1, cases where there was an insoluble or insoluble portion are indicated as "insoluble," and cases where there was no insoluble portion are indicated as "soluble."

[0250] Solvent 1: Aqueous tetramethylammonium hydroxide solution (2.38%) It was confirmed that Resins 1 to 9 were soluble in alkaline solutions.

[0251]

[0252] <Evaluation of liquid repellency (water repellency and oil repellency)> Washed and dried 30 x 30 mm ２A 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 resins 6 and 7, or a mixed solution of resins 6 and 9 (resin 6: 2 wt%, resin 7 or resin 9: 20 wt%, solvent: propylene glycol monomethyl ether acetate: 78 wt%) was spin-coated onto glass (Corning Eagle XG) at 500 rpm for 5 seconds and 1500 rpm for 20 seconds. UV irradiation was performed at 2000 mJ / cm. ２ The contact angles with water, diiodomethane, m-xylene, and tetralin were measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name DM-300) by the θ / 2 method. The results are shown in Table 2.

[0253] 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 exhibit excellent liquid repellency.

[0254]

[0255] <Curability (Crosslinkability) and Pattern Formation Evaluation> For the curability evaluation, solutions were prepared by dissolving each of Resins 1 to 9, a mixture of Resins 6 and 7, a mixture of Resins 6 and 9, and Resin A in the solvent and under the sensitizer addition conditions shown in Table 3. After that, washed and dried 30 × 30 mm ２ A film was formed on a glass substrate (Corning Eagle XG) using a spin coater under conditions of 500 rpm x 5 seconds and 1500 rpm x 20 seconds, and then thoroughly dried. ２ The resin film was photocrosslinked by irradiating it with UV. The thickness of this film was measured using a DektakXT stylus profiler manufactured by Bruker. ０ Next, the glass plate coated with this photo-crosslinked resin film was immersed for 1 minute in a tetramethylammonium hydroxide aqueous solution (2.38%), which is a good solvent for resins, and then removed and dried on a hot plate at 150°C for 10 minutes, after which the film thickness was measured and determined as T １ Using these measured film thickness values, the remaining film ratio (R) was calculated according to the following formula.

[0256] R=T １ / T ０ × 100 (%) The photocrosslinking (curing) property was evaluated using a residual film rate (R) of 95% or more as the criterion for crosslinking. The lower the UV irradiation dose required to achieve a residual film rate of 95% or more, the higher (faster) the photocrosslinking property. ２ When R 95% or more was achieved at the following UV irradiation doses, it was judged to be "crosslinked."

[0257] For the pattern formation evaluation, a mask was used as the pattern formation mask, which was patterned with chrome and had a shape in which 10 squares, each 50 μm on a side, were arranged vertically and 10 squares horizontally. ２ The solution was spin-coated on a glass substrate, and a mask was placed on the film obtained. The film was then irradiated with a UV dose that resulted in a residual film rate of 95% or more in a curing evaluation. After irradiation, the uncrosslinked portions were washed away with a tetramethylammonium hydroxide aqueous solution (2.38%) for 1 minute, leaving a 10 × 10 μm ２ Size: 50 × 50 μm ２ It was confirmed using a laser microscope whether or not a pattern with 100 vacant spaces of each size had been formed.

[0258] Solvent 2: N,N-dimethylformamide Solvent 3: propylene glycol monomethyl ether acetate Sensitizer 1: 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Co., Ltd.)

[0259] Resins 1 to 9, a mixture of resins 6 and 7, and a mixture of resins 6 and 9 were 1000 mJ / cm ２ The remaining film rate was 95% or more, showing excellent photocurability. On the other hand, Resin A was insoluble in an aqueous tetramethylammonium hydroxide solution (2.38%), and therefore could not be evaluated.

[0260] Resins 1 to 9, a mixture of resins 6 and 7, and a mixture of resins 6 and 9 all formed patterns, demonstrating excellent patterning properties. However, resin A was insoluble in an aqueous solution of tetramethylammonium hydroxide (2.38%), and therefore could not be patterned.

[0261]

[0262] REFERENCE SIGNS LIST 1 organic semiconductor layer 2 substrate 3 gate electrode 4 gate insulating layer 5 source electrode 6 drain electrode 7 pattern 8 protective film layer

Claims

1. A repeating unit represented by the following formula (1) containing a photocrosslinkable group, Repeating units containing fluorine atoms, A resin containing one or more units selected from the group consisting of repeating units containing acidic functional groups and repeating units containing hydrophilic functional groups. 【Chemistry 1】 (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６ (m represents an integer greater than or equal to 3, and n represents an integer less than or equal to m.)

2. The resin according to claim 1, wherein the resin contains repeating units comprising a functional group selected from a carboxyl group, a sulfo 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 units comprising the acidic functional group and the repeating units comprising the 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 units containing the acidic functional group and the repeating unit containing the hydrophilic functional group. 【Chemistry 2】 (In formula (a), R ９ represents a hydrogen atom or a methyl group. L ３ 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 the fluorine atom. 【Transformation 3】 (In formula (2), R ７ L represents a hydrogen atom or a methyl group. ２ Rf represents a single bond or a divalent linking group. １ (This represents one of the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched fluoroalkyl group having 3 to 15 carbon atoms, or a cyclic fluoroalkyl group having 3 to 15 carbon atoms.)

5. The resin according to claim 1 or 2, wherein in formula (1), A is one type of linking group from the group consisting of the following formulas (a-1) to (a-4). 【Chemistry 4】 (In equations (a-1) to (a-4), *L is the same as L in equation (1) above. １ The bond position is shown, and the asterisk (*) at the end of the carbon atom indicates the bond position with the oxygen atom constituting the ester group in formula (1) above.

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

7. The resin according to claim 1 or 2, which is soluble in an alkaline solution.

8. A composition comprising the resin described in claim 1 and at least one of an organic solvent and a fluorine-based solvent.

9. A photocrosslinked product of the resin according to claim 1 or 2 or the composition according to claim 8.

10. A pattern composed of the photocrosslinked material described in claim 9.

11. An electronic device comprising the photocrosslinked material described in claim 9.

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