Photocrosslinkable polymer, insulating film and organic field effect transistor device including the same

Abstract

To provide a resin which enables manufacture of an organic electric field effect transistor device element having excellent bias stress resistance by using as a gate insulation film layer of an organic electric field effect transistor device.SOLUTION: A resin includes a repeating unit represented by the following formula, wherein a HOMO level that the repeating unit represented by the following formula has is -6.4 eV or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin that, when used as a gate insulating film layer in an organic field effect transistor device, provides an organic field effect transistor device element with excellent bias stress resistance. [Background technology]

[0002] Organic field-effect transistor devices can be fabricated by coating solutions containing organic materials or forming films using printing methods, and are attracting attention because of the potential for low-cost production of large numbers of devices on large-area substrates.

[0003] A technology has been disclosed for using a photocrosslinkable polymer as a polymer dielectric layer (insulating film layer) for an organic field-effect transistor device, in which a compound having a photocrosslinkable group is introduced into an aromatic vinyl polymer such as polystyrene or poly-α-methylstyrene by the Friedel-Crafts acylation reaction (see, for example, Patent Document 1).

[0004] In recent years, polymer dielectric layers with excellent bias stress resistance have been desired from the viewpoint of reliability and stability of organic field-effect transistor devices. It is generally known that the threshold voltage of organic field-effect transistor devices changes when a constant bias voltage is applied for a long period of time, and it is preferable that the amount of threshold voltage change due to bias stress be 2 V or less. Various causes of this change are thought to be involved, including environmental factors such as atmospheric oxidation and moisture, as well as factors such as the crystalline structure and defects of the organic semiconductor. However, one of the main causes is thought to be carrier trapping, in which carriers formed in the semiconductor layer are captured in the polymer dielectric layer (insulating film layer) (see, for example, Non-Patent Document 1).

[0005] The present inventors have conducted research and found that in recent years, there has been a demand for a bias stress resistance higher than that of an organic field effect transistor device element having a gate insulating film layer made of the resin described in Patent Document 1. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-154814 [Non-patent literature]

[0007] [Non-Patent Document 1] Advanced Materials Journal, Vol. 26, p. 1660 (2014) Summary of the Invention [Problem to be solved by the invention]

[0008] 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 can be used as a gate insulating film layer of an organic field-effect transistor device to produce an organic field-effect transistor device element having excellent bias stress resistance. [Means for solving the problem]

[0009] As a result of extensive research to solve the above problems, the present inventors have discovered that deepening the HOMO level of a resin (insulating film layer) increases the energy barrier when carriers generated in the organic semiconductor layer are captured by the resin, thereby suppressing carrier trapping and effectively improving mobility and bias stress resistance, and that a specific resin is excellent in the mobility and bias stress resistance required for an insulating film, leading to the completion of the present invention.

[0010] That is, the present invention relates to a resin containing repeating units represented by formula (1) and formula (2), wherein the repeating units represented by formula (2) have a HOMO level of −6.4 eV or less and the repeating units of formula (2) account for 20 mol % or more of the total number of repeating units of formula (1) and formula (2), an insulating film using the resin, and an organic field-effect transistor device using the insulating film.

[0011] [ka]

[0012] (1) (In formula (1), R1 represents hydrogen or a C1-C6 alkyl group, S1 represents -O- or -C(O)-, p represents 0 or 1, A1 represents a C6-C19 aryl group, and Y represents a halogen, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group. In addition, k represents an integer of 0 to (s-1), where s represents the number of carbon atoms constituting A1.)

[0013] [ka]

[0014] (2) (In formula (2), R2 represents hydrogen or a C1 to C6 alkyl group, S2 represents -O- or -C(O)-, q represents 0 or 1, A2 represents a C6 to C19 aryl group, Y represents a substituent defined in formula (1), j represents an integer of 0 to (r-2), and m represents an integer of 1 to (rj-1). Here, r represents the number of carbon atoms constituting A2. Furthermore, Z represents at least one organic group selected from formulas (A) to (D).)

[0015] [ka]

[0016] (A)

[0017] [ka]

[0018] (B)

[0019] [ka]

[0020] (C)

[0021] [ka]

[0022] (D) (In formulas (A) to (D), R2 and R3 each independently represent hydrogen, halogen, a C1 to C6 alkyl group, an aryl group, or a carboxyalkyl group; R4 to R 28 each independently represents hydrogen, halogen, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1 to C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group. The present invention will be described in detail below.

[0023] The resin of the present invention comprises repeating units of formula (1) and formula (2) above.

[0024] In formula (1), R1 represents hydrogen or a C1 to C6 alkyl group, preferably hydrogen.

[0025] The C1 to C6 alkyl group in R1 in formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0026] In formula (1), S1 represents —O— or —C(O)—.

[0027] In formula (1), p represents 0 or 1, with 0 being preferred.

[0028] In formula (1), A1 represents a C6 to C19 aryl group.

[0029] The C6 to C19 aryl group in A1 in formula (1) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group, with a phenyl group being preferred.

[0030] In formula (1), Y represents a halogen, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1 to C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group.

[0031] The halogen in Y in formula (1) is not particularly limited, and examples thereof include chlorine, fluorine, and bromine.

[0032] The carboxyalkyl group for Y in formula (1) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.

[0033] The alkyl ether group for Y in formula (1) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.

[0034] The C1 to C18 alkyl group for Y in formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0035] The fluoroalkyl group for Y in formula (1) is not particularly limited, and examples thereof include a 1,1,1-trifluoroethyl group, a 1,1,1,2,2-pentafluoropropyl group, a 1,1,1,2,2,3,3-heptafluorobutyl group, a trifluoromethyl group, and a pentafluoroethyl group.

[0036] The cycloalkyl group represented by Y in formula (1) is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. In formula (1), k represents an integer of 0 to (s-1), and is preferably 0. Here, s represents the number of carbon atoms constituting A1.

[0037] In formula (2), R2 represents hydrogen or a C1 to C6 alkyl group, preferably hydrogen.

[0038] The C1 to C6 alkyl group in R2 in formula (2) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0039] In formula (2), S2 represents —O— or —C(O)—.

[0040] In formula (2), q represents 0 or 1, with 0 being preferred.

[0041] In formula (2), A2 represents a C6 to C19 aryl group.

[0042] The C6 to C19 aryl group in A2 in formula (2) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthranyl group, and a biphenyl group, with a phenyl group being preferred.

[0043] In formula (2), Y represents a substituent similar to the substituent defined in formula (1).

[0044] In formula (2), m represents an integer of 1 to (rj-1), where r represents the number of carbon atoms constituting A2, and j represents an integer of 0 to (r-2).

[0045] In formula (2), Z represents at least one organic group selected from formulae (A) to (D), with (A) being preferred.

[0046] In formulas (A) to (D), R2 and R3 each independently represent hydrogen, halogen, a C1 to C6 alkyl group, an aryl group, or a carboxyalkyl group, preferably hydrogen, and R4 to R 28 each independently represents hydrogen, halogen, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, C1 to C18 alkyl group, fluoroalkyl group, or cycloalkyl group, and among these, halogen, nitro group, or fluoroalkyl group is preferred.

[0047] The halogen in R2 and R3 in formulas (A) to (D) is not particularly limited, and examples thereof include chlorine, fluorine, and bromine.

[0048] The C1 to C6 alkyl group in R2 and R3 in formulas (A) to (D) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0049] The aryl group in R2 and R3 in formulae (A) to (D) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

[0050] The carboxyalkyl group in R2 and R3 in formulae (A) to (D) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.

[0051] R4 to R in formula (A) to formula (D) 28 The halogen in is not particularly limited, and examples thereof include chlorine, fluorine, and bromine, with chlorine and fluorine being preferred.

[0052] R4 to R in formula (A) to formula (D) 28 The carboxyalkyl group in is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.

[0053] R4 to R in formula (A) to formula (D) 28 The alkyl ether group in is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.

[0054] R4 to R in formula (A) to formula (D) 28 The aryl ether group in is not particularly limited, and examples thereof include a phenoxy group, a p-methylphenoxy group, a p-ethylphenoxy group, and a p-methoxyphenoxy group.

[0055] R4 to R in formula (A) to formula (D) 28 The C1 to C18 alkyl group in is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-hexyl group, an n-decyl group, and an n-octadecyl group.

[0056] R4 to R in formula (A) to formula (D) 28 The fluoroalkyl group in is not particularly limited, and examples thereof include a 1,1,1-trifluoroethyl group, a 1,1,1,2,2-pentafluoropropyl group, a 1,1,1,2,2,3,3-heptafluorobutyl group, a trifluoromethyl group, a pentafluoroethyl group, and the like, with a trifluoromethyl group being preferred.

[0057] R4 to R in formula (A) to formula (D) 28 The cycloalkyl group in is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0058] Specific examples of the organic group represented by formula (A) include the following.

[0059] [ka]

[0060] Among them, the organic groups represented by the following are preferred:

[0061] [ka]

[0062] In particular, the organic groups shown below are preferred.

[0063] [ka]

[0064] Specific examples of the organic group represented by formula (B) include the following:

[0065] [ka]

[0066] Specific examples of the organic group represented by formula (C) include the following.

[0067] [ka]

[0068] Specific examples of the organic group represented by formula (D) include the following.

[0069] [ka]

[0070] In the resin of the present invention, the HOMO level of the repeating unit represented by formula (2) is −6.4 eV or less, preferably −6.5 eV or less, and particularly preferably −7.00 to −6.5 eV.

[0071] The HOMO level is usually a concept that represents the energy level of the orbital of a single molecule, but in this specification, the HOMO level of a compound in which the repeating end of the repeating unit is replaced with a hydrogen atom is defined as the HOMO level of that repeating unit.

[0072] In this specification, the HOMO energy level was calculated using the quantum chemical calculation Gaussian. The calculation conditions were as follows: B3LYP was used as the density functional for atomic orbitals, 6-31G(d,p) was used as the basis set, and Gaussian09W was used as the program.

[0073] In order to set the HOMO level at -6.4 eV or less, the repeating unit represented by formula (2) has at least one halogen, cyano group, nitro group, carboxyalkyl group, or fluoroalkyl group.

[0074] The resin of the present invention containing repeating units represented by formula (1) and formula (2) contains repeating units of formula (2) in an amount of 20 mol % or more, preferably 40 mol % or more, particularly preferably 70 mol % or more, based on the total number of repeating units of formula (1) and formula (2).

[0075] In the present invention, there is no limitation on the molecular weight of the resin having the repeating units of formula (1) and formula (2), and for example, a molecular weight of 200 to 10,000,000 (g / mol) can be used. 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).

[0076] Furthermore, the polymer molecules of the resins containing the repeating units of formula (1) and formula (2) may contain a structure based on the cyclization of a photoreactive group, as long as the solubility is not impaired.

[0077] Examples of the structure based on the cyclization of the photoreactive group include structures represented by the following formulas (3) to (10).

[0078] [ka]

[0079] (3)

[0080] [ka]

[0081] (4)

[0082] [ka]

[0083] (5)

[0084] [ka]

[0085] (6)

[0086] [ka]

[0087] (7)

[0088] [ka]

[0089] (8)

[0090] [ka]

[0091] (9)

[0092] [ka]

[0093] (10) (In formulas (3) to (10), R2 to R 28 is the same as defined in formulas (A) to (D). Furthermore, the resin having the repeating units of formula (1) and formula (2) may contain, for example, a dimer of a photoreactive group as shown below.

[0094] Examples of the dimer of the photoreactive group include structures represented by the following formulas (11) to (13).

[0095] [ka]

[0096] (11)

[0097] [ka]

[0098] (12)

[0099] [ka]

[0100] (13) (In Equation (11), Equation (12), and Equation (13), R2 to R 25 are the same as defined in Formulae (A) to (C), a, b, and c represent integers of 0 to 4, and R A represents a substituents selected from R4 to R8 defined in formula (A), R B is R defined in formula (B) 13 ~R 17 b substituents selected from R C is R defined in formula (C) 22 ~R 25 represents c substituents selected from The resin of the present invention has repeating units of formula (1) and formula (2) above, and may have repeating units other than those of formula (1) and formula (2) as long as the effects of the present invention are not impaired. Examples of repeating units other than those of formula (1) and formula (2) include butadiene, ethylene, propylene, acrylonitrile, alkyl acrylate, alkyl methacrylate, α-phenylalkyl acrylate, maleic anhydride, acrylic acid, 4-vinylpyridine, trans-1,3-pentadiene, p-acetoxystyrene, vinyl-tris(trimethoxysiloxy)silane, vinyl benzoate, vinyl butyl ether, and phenyl vinyl ketone, with ethylene and propylene being preferred.

[0101] The resins having the repeating units of formula (1) and formula (2) of the present invention can be produced by introducing a photocyclizable compound into an aromatic group-containing polymer via the Friedel-Crafts acylation reaction.

[0102] In the present invention, examples of photocyclizable compounds include cinnamic acid chloride compounds represented by the following formula (14), phenylethenylbenzoic acid chloride compounds represented by the following formula (15), pyridinylethenylbenzoic acid chloride compounds represented by the following formula (16), and coumarin-6-carboxylic acid chloride compounds represented by the following formula (17). Among these, the cinnamic acid chloride compound represented by the following formula (14) is preferred because it is easy to produce. Furthermore, these compounds can be used in combination of two or more types, if necessary.

[0103] [ka]

[0104] (14)

[0105] [ka]

[0106] (15)

[0107] [ka]

[0108] (16)

[0109] [ka]

[0110] (17) (In formulas (14) to (17), R2 to R 28 is the same as defined in formulas (A) to (D). The aromatic group-containing polymers into which photoreactive groups can be introduced by the Friedel-Crafts acylation reaction are not limited as long as they are inert to the reaction catalysts described below. Examples include polystyrenes such as poly-α-methylstyrene, poly-p-methoxystyrene, and syndiopolystyrene; polyvinyl aryl ketones such as polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl anthracene, polyvinyl carbazole, and polyvinyl phenyl ketone; styrene-butadiene copolymers; ethylene-styrene copolymers; ethylene-propylene-styrene copolymers; styrene-acrylonitrile copolymers; styrene-alkyl acrylate copolymers; styrene-alkyl methacrylate copolymers; styrene-α-phenyl alkyl acrylate copolymers; styrene- Examples of suitable polymers include maleic anhydride copolymers, styrene-acrylic acid copolymers, styrene-4-vinylpyridine copolymers, styrene-trans-1,3-pentadiene copolymers, styrene-2,4,6-trimethylstyrene copolymers, styrene-p-acetoxystyrene copolymers, styrene-vinyl-tris(trimethoxysiloxy)silane copolymers, styrene-vinylbenzoate copolymers, styrene-vinylbutyl ether copolymers, polyaryl vinyl ketones such as polyphenyl vinyl ketone, and petroleum resins. However, to reduce the dielectric constant and leakage current, polymers composed solely of aromatic and aliphatic hydrocarbons, such as polystyrene, ethylene-styrene copolymers, and ethylene-propylene-styrene copolymers, are preferred. These copolymers can also be used in combination.

[0111] The amount of the photocyclizable compound added to the aromatic group-containing polymer into which the photoreactive group is introduced by the Friedel-Crafts acylation reaction is preferably 0.2 to 5.0 mol, more preferably 1.0 to 3.0 mol, per mol of aromatic group contained in the aromatic group-containing polymer, in order to improve the solubility in organic solvents and storage stability of the resulting resin. The amount of photoreactive group introduced to the aromatic group in the reaction is preferably 0.2 to 1.0 mol, more preferably 0.4 to 1.0 mol, per mol of aromatic group contained in the resin, in terms of solubility in organic solvents, storage stability, ease of photocrosslinking, and solvent resistance (crack resistance) of the resin layer after photocrosslinking.

[0112] The Friedel-Crafts acylation reaction can be carried out using a reaction catalyst.

[0113] In the present invention, it is preferable to use a known super strong acid as the reaction catalyst, and there is no limitation as long as it is a super strong acid, and examples thereof include trifluoromethanesulfonic acid, fluorosulfonic acid, fluoroantimonic acid, and carborane acid. The amount of the reaction catalyst added is preferably 0.1 to 3.0 times by mole per mole of the photocyclizable compound, in order to avoid a complicated neutralization operation after the reaction and to prevent a decrease in the reaction rate.

[0114] The Friedel-Crafts acylation reaction is exothermic and may induce a side reaction in which photoreactive groups are crosslinked by heating in the reaction system. Therefore, in the present invention, a solution reaction, which allows for easy reaction temperature control, is preferred to suppress this side reaction. The reaction solvent used in the solution reaction in the present invention can be any solvent stable to the Friedel-Crafts reaction. Suitable examples of suitable solvents include fully dehydrated chlorinated hydrocarbon solvents, fluorinated solvents, aliphatic hydrocarbon solvents, sulfur-containing solvents, and nitrile-based solvents that are inert to the reaction. Examples of suitable chlorinated hydrocarbon solvents include methylene chloride, carbon tetrachloride, 1,1,2-trichloroethane, and chloroform. Examples of suitable fluorinated solvents include Zeorola H. Examples of suitable aliphatic hydrocarbon solvents include cyclohexane. Examples of suitable sulfur-containing solvents include carbon disulfide, sulfone dimethyl sulfoxide, dimethyl sulfate, and dimethyl sulfone. Examples of suitable nitrile-based solvents include acetonitrile.

[0115] The reaction temperature for the Friedel-Crafts acylation reaction is not particularly limited, but from the viewpoint of economic efficiency in terms of cooling and heating, a temperature of 0 to 40° C. If necessary, the reaction can be carried out at the reflux temperature of the solvent used, but a temperature of less than 200° C. is preferred.

[0116] In the Friedel-Crafts acylation reaction, the reaction time is not particularly limited and may be, for example, 1 to 100 hours. From the viewpoints of reaction rate and economic efficiency, it is preferably 2 to 20 hours.

[0117] A film can be formed by dissolving a resin containing the repeating units of the above formula (1) and (2) of the present invention in a solvent and coating or printing the solution on various substrates.

[0118] The solvent can be any solvent that dissolves the resin, and examples thereof include aromatic hydrocarbons such as cyclohexane, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, N-hexylbenzene, tetralin, decalin, isopropylbenzene, and chlorobenzene; chlorinated aliphatic hydrocarbon compounds such as methylene chloride and 1,1,2-trichloroethylene; aliphatic cyclic ether compounds such as tetrahydrofuran and dioxane; ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone; ester compounds such as ethyl acetate, dimethyl phthalate, methyl salicylate, amyl acetate, and 2-methoxy-1-methylethyl acetate; alcohols such as n-butanol, ethanol, and isobutanol; 1-nitropropane, carbon disulfide, and limonene. These solvents can be mixed and used as needed.

[0119] Examples of substrates include inorganic material substrates such as glass, quartz, aluminum oxide, hydrodoped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; and surface-coated nonwoven fabrics. Examples of plastics include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, and ethylene-vinyl acetate. Examples of the polymerizable monomer include vinyl 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 ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, and styrene block copolymer.

[0120] When coating or printing on a substrate, the resin according to the present invention can be coated or printed using, for example, spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, float coating, gravure printing, flexographic printing, screen printing, inkjet printing, letterpress reverse printing, etc. Since the film of the present invention is formed using these methods, it is necessary for the film of the present invention to have excellent solubility in general-purpose solvents.

[0121] Films using resins containing the repeating units of formula (1) and formula (2) of the present invention can be used as insulating films, either as they are formed or, if necessary, as crosslinked products obtained by photocrosslinking (photocyclization). In the present invention, if the insulating film is formed and then used as an insulating film without being photocrosslinked, it must have good solubility in the general-purpose solvent used to form the insulating film, and must also be capable of forming an organic semiconductor layer on top of the insulating film using a solvent different from the general-purpose solvent. In this case, if the film has solvent resistance (crack resistance) to the organic semiconductor solution, it can be used as an insulating film as it is. However, if the film does not have excellent solvent resistance (crack resistance), it cannot be formed by printing, and must be formed by a method such as vapor deposition, which is less economical than printing.

[0122] When the resin according to the present invention is used as an insulating film, radiation is used for photocrosslinking (photocyclization), for example, ultraviolet light with a wavelength of 245 to 350 nm. The irradiation dose is appropriately changed depending on the composition of the resin, but is, for example, 50 to 3000 mJ / cm. 2 In order to prevent a decrease in the degree of crosslinking and improve economic efficiency by shortening the process time, the dose is preferably 50 to 1000 mJ / cm. 2The ultraviolet irradiation is usually carried out in the atmosphere, but can also be carried out in an inert gas or in a certain amount of inert gas flow, if necessary. If necessary, a photosensitizer can be added to promote the photocrosslinking reaction. There are no limitations on the photosensitizer used, and examples include benzophenone compounds, anthracene compounds, anthraquinone compounds, thioxanthone compounds, and nitrophenyl compounds. Benzophenone compounds are preferred because they are highly compatible with the resin used in the present invention. Furthermore, two or more types of sensitizers can be used in combination, if necessary.

[0123] An insulating film containing the crosslinked resin of the present invention can be formed and used as a gate insulating layer in an organic field-effect transistor device (OFET). The organic field-effect transistor device can be obtained, for example, by laminating an organic semiconductor layer provided with a source electrode and a drain electrode, and a gate electrode on a substrate via the gate insulating layer.

[0124] From the viewpoint of practicality as an organic field-effect transistor device (OFET), the mobility of the OFET device is 0.20 cm 2 It is preferable that the value is equal to or greater than / Vs.

[0125] From the viewpoint of device reliability, the bias stress resistance of an organic field effect transistor device is preferably such that the shift in threshold voltage is 2 V or less when a bias voltage is applied for 1 hour.

[0126] In the present invention, the organic field-effect transistor device (OFET) may be any of the following types: bottom-gate bottom-contact (BGBC) type, bottom-gate top-contact (BGTC) type, top-gate bottom-contact (TGBC) type, and top-gate top-contact (TGTC) type. Among these various types of organic field-effect transistor devices, for example, the structure of a bottom-gate bottom-contact (BGBC) type device is shown in Figure 1.

[0127] The substrate that can be used in the OFET is not particularly limited as long as it has sufficient flatness to fabricate the device, and examples thereof include inorganic material substrates such as glass, quartz, aluminum oxide, hydrodoped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; and surface-coated nonwoven fabrics. Composite materials made of these materials or multilayered materials of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

[0128] 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), polyether sulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, and styrene block copolymer. Furthermore, two or more of the above plastics can be laminated to form a substrate.

[0129] Examples of conductive gate electrodes, source electrodes, or drain electrodes that can be used in the present invention include conductive materials such as gold, silver, aluminum, copper, titanium, platinum, chromium, polysilicon, silicide, indium tin oxide (ITO), tin oxide, etc. Furthermore, a plurality of these conductive materials can also be stacked and used.

[0130] In addition, in a BGTC-type element, an electrode is formed on the substrate or the organic semiconductor layer. In this case, the method for forming the electrode is not particularly limited, and examples thereof include vapor deposition, high-frequency sputtering, and electron beam sputtering. Alternatively, methods such as solution spin coating, drop casting, dip coating, doctor blade printing, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, inkjet printing, and letterpress reverse printing can also be employed using an ink in which nanoparticles of the conductive material are dissolved in water or an organic solvent. If necessary, a treatment for adsorbing fluoroalkylthiol, fluoroarylthiol, or the like onto the electrode may be performed.

[0131] There is no limitation on the organic semiconductor that can be used as a raw material for the organic semiconductor layer in the present invention, and both N-type and P-type organic semiconductors can be used. They can also be used as bipolar organic field effect transistor devices that combine N-type and P-type, and examples thereof include those represented by formulas (F-1) to (F-10).

[0132] [ka]

[0133] (F-1)

[0134] [ka]

[0135] (F-2)

[0136] [ka]

[0137] (F-3)

[0138] [ka]

[0139] (F-4)

[0140] [ka]

[0141] (F-5)

[0142] [ka]

[0143] (F-6)

[0144] [ka]

[0145] (F-7)

[0146] [ka]

[0147] (F-8)

[0148] [ka]

[0149] (F-9)

[0150] [ka]

[0151] (F-10) Among these (F-1) to (F-10), (F-2), (F-3) and (F-10) are preferred, with (F-10) being particularly preferred.

[0152] In the present invention, both low-molecular-weight and high-molecular-weight organic semiconductors can be used, and a mixture of these can also be used.

[0153] 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 the organic semiconductor layer. When coating or printing using a solution in which the organic semiconductor layer is dissolved in an organic solvent, the solution concentration varies depending on the structure of the organic semiconductor and the solvent used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the layer thickness, it is preferably 0.2 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, 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- 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 mono 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, 1,1,2,2-tetrachloroethane, Chloroform, Dichloromethane, Tetrahydrofuran, 1,2-dimethoxyethane, Dioxane Examples of suitable solvents include toluene, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. However, to obtain a crystal film with desirable properties, a solvent with a high dissolving power for organic semiconductors and a boiling point of 100°C or higher is suitable, and preferred solvents are toluene, xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol. Mixed solvents containing two or more of the above solvents in appropriate ratios can also be used.

[0154] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles can be added to the organic semiconductor layer as needed, either as solids or as dispersions of nanoparticles in water or organic solvents, and a protective film can be formed by coating the above-mentioned gate insulating layer with the polymer solution.Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied to this protective film as needed. [Effects of the Invention]

[0155] The present invention provides a resin that can be used as a gate insulating film layer of an organic field effect transistor device to produce an organic field effect transistor device element having excellent bias stress resistance. [Brief explanation of the drawings]

[0156] [Figure 1] ; A diagram showing the cross-sectional shape of a bottom gate-bottom contact (BGBC) type element. [Figure 2] FIG. 1 shows the 1H-NMR chart of Resin 1 produced in Example 1. [Figure 3] FIG. 1 shows that the OFET device fabricated in Example 1 shows only a slight change in transfer characteristics (Id-Vg) before and after applying a gate voltage (Vg) of −30 V continuously for 1 hour, demonstrating excellent bias stress resistance. [Figure 4] FIG. 10 shows that the transfer characteristics (Id-Vg) of the OFET device fabricated in Comparative Example 1 change significantly before and after applying a gate voltage (Vg) of −30 V continuously for 1 hour. [Example]

[0157] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The organic semiconductor (di-n-hexyldithienobenzodithiophene) used in the examples was synthesized according to the manufacturing method described in JP 2015-224238 A.

[0158] In the examples, NMR, spin coating, film thickness measurement, ultraviolet (UV) irradiation, vacuum deposition, UV irradiation dose required for crosslinking, evaluation of transfer characteristics of OFET devices, and evaluation of bias stress resistance were performed under the following conditions and with the following equipment. <nmr> 1 The measurement of the 1H-NMR spectrum was carried out using a JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.). <Spin-coating> As the spin-coating apparatus, MS-A100 manufactured by Mikasa Co., Ltd. was used. <Film thickness measurement> Measurement was carried out using a DektakXT stylus profiler manufactured by Bruker. <UV irradiation> Using a UV mask aligner, UPE-1605MA manufactured by USHIO Lighting Co., Ltd., UV irradiation was carried out under the condition of a UV intensity of 14.2 mW / cm 2 of 2. <Vacuum evaporation> A small vacuum evaporation apparatus VTR-350M / ERH manufactured by Ulvac Kiko Co., Ltd. was used. <Transfer characteristic evaluation and bias stress resistance evaluation> A bottom-gate·bottom-contact (BGBC) type element, which is a form of an organic field-effect transistor device, was fabricated. Using a semiconductor parameter analyzer 4200-SCS manufactured by Keysight Technologies, with the source-drain voltage (Vd) of the BGBC type FET element set to -15 V, the gate voltage (Vg) was scanned, the transfer characteristics (Id-Vg) before applying the bias voltage were measured, and the mobility was evaluated. Then, after continuously applying a gate voltage (Vg) of -30 V for 1 hour as the bias voltage, measurement was carried out under the same conditions, and the absolute value of the change amount of the threshold voltage before and after applying the bias voltage was evaluated from the obtained transfer characteristics.

[0159] The synthesis of Resins 1 to 9 is shown below. All reactions, purification, and drying were carried out under yellow light or in the dark. In the synthesis, performing under yellow light or in the dark is to prevent the photocyclization reaction of the photocyclizable compound and the photocyclization reaction of the resin into which the photocyclizable compound is introduced. (Example 1) <Synthesis of Resin 1> 8.3 g (38.4 mmol) of 3-(trifluoromethyl)cinnamic acid (Tokyo Chemical Industry Co., Ltd.) was weighed into a 200 mL Schlenk flask, a reflux tube was attached, and the atmosphere was replaced with nitrogen. A catalytic amount of DMF (Fujifilm Wako Pure Chemical Industries, Ltd.), 33 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.), and 8.3 mL (115 mmol) of thionyl chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were sequentially charged using a syringe. The mixture was then refluxed at 50°C in a water bath and stirred for 4 hours. The mixture was then removed from the heat and allowed to cool to room temperature. The solvent was then completely removed by drying under reduced pressure for approximately 1 hour, yielding 3-(trifluoromethyl)cinnamic acid chloride.

[0160] After synthesis, 2.0 g of polystyrene (DIC) with a weight-average molecular weight of 55,000, 27 mL of dichloromethane, and 27 mL of Zeorola H (Zeon Chemical) were charged into the Schlenk flask and dissolved at room temperature with stirring. The Schlenk flask was placed in an ice bath for at least 30 minutes to sufficiently cool the solution, and then 8.7 g (38.4 mmol) of trifluoromethanesulfonic acid (Wako Pure Chemical Industries, Fujifilm) was slowly added dropwise with a syringe while stirring. The polymer solution turned reddish-purple as it was added. After the addition, the mixture was stirred in an ice bath for one hour, and then allowed to react at room temperature for five hours. The reaction solution was then cannulated into a saturated aqueous solution of sodium bicarbonate to neutralize the trifluoromethanesulfonic acid and hydrochloric acid in the system. The aqueous layer of the neutralized solution was removed by decantation, and the dichloromethane layer was separated. Water was added again, and the aqueous layer was removed by decantation. This procedure was repeated twice to remove excess sodium bicarbonate. The decanted solution was reprecipitated with 430 mL of methanol, and the polymer was isolated by filtration twice. After drying under reduced pressure at 50°C, 4.9 g (85% yield) of Resin 1 was obtained.

[0161] 1 As a result of analysis by 1 H-NMR, it was confirmed that the obtained resin 1 (formula below) contained 21 mol % and 79 mol % of structural units represented by formula (1) and formula (2), respectively.

[0162] [ka]

[0163] Incidentally, the 1 1H-NMR chart of Resin 1 is shown in Fig. 2. 1 1H-NMR (400 MHz, CDCl3): δ 7.60 (brs, -CH=CH-Ph), 7.45~6.46 (m, aromatic, -CH=CH-Ph), 2.05 (brs, -CH2-CH-), 1.73~1.42 (bm, -CH2-) <Fabrication and Evaluation of FET Device> Silver was vacuum-evaporated onto a cleaned and dried 30×30 mm 2 glass (substrate) (Eagle XG manufactured by Corning) to form a gate electrode with a thickness of 50 nm. On the substrate on which the electrode was formed, a 2-methoxy-1-methylethyl acetate solution (11 wt%) of the obtained Resin 1 was spin-coated under the conditions of 500 rpm × 5 s and 2000 rpm × 20 s, and after drying at 50 °C for 1 minute (formation of an insulating film), ultraviolet rays of 100 mJ / cm 2 were irradiated to form a gate insulating layer with a crosslinked film thickness of 500 nm. Gold was vacuum-evaporated onto the substrate on which the gate electrode and the gate insulating layer were formed to form a source electrode and a drain electrode with a thickness of 50 nm, a channel length of 100 μm, and an electrode width of 500 μm. Then, it was immediately immersed in an isopropanol solution of 30 mmol of pentafluorobenzenethiol, taken out after 5 minutes, washed with isopropanol, and then blown dry. Then, 220 μL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithieno[3,2-b:2′,3′-d]benzo[1,2-d:4,5-d′]dithiophene) was dropped, and after standing for 15 hours in a constant-temperature dark room, the solvent was volatilized by heating at 40 °C for 3 hours to form a semiconductor layer by drop-casting. By the above method, a bottom-gate·bottom-contact (BGBC) type organic field-effect transistor device was fabricated.

[0164] Table 1 shows the results of the evaluation of the HOMO level of the repeating unit represented by Formula (2) in the composition of the synthesized resin, the mobility of the fabricated organic field-effect transistor device, and the bias stress resistance.

[0165]

Table 1

[0166] The source-drain voltage (Vd) was set to -15V, and the gate voltage (Vg) was scanned to measure the transfer characteristics (Id-Vg) before applying the bias voltage. The mobility was found to be 0.23 cm 2 / V·s, demonstrating excellent mobility. After that, a gate voltage (Vg) of -30V was continuously applied for 1 hour, and measurements were then performed under the same conditions. From the obtained transfer characteristics, the change in threshold voltage before and after bias voltage application was evaluated. The change in threshold voltage was 1.0V, demonstrating excellent bias stress tolerance. Figure 3 shows the transfer characteristics before and after bias stress application. Example 2 Resin 2 (4.3 g, 89% yield) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with 2-(trifluoromethyl)cinnamic acid (Tokyo Chemical Industry Co., Ltd.).

[0167] 1 As a result of analysis by 1 H-NMR, it was confirmed that the resulting resin 2 (formula below) contained 26 mol % and 74 mol % of structural units represented by formula (1) and formula (2), respectively.

[0168] [ka]

[0169] 1 H-NMR (400MHz, CDCl3): δ7.60(brs,-CH=CH-Ph),7.99~6.46(m,aromatic,-CH=CH-Ph),2.05(brs,-CH2-CH-),1.73~1.42(bm,-CH2-) Using the obtained resin 2, the UV irradiation dose was 500 mJ / cm 2 An insulating film was formed using the same method as in Example 1, except that the resin was changed to 2 / V·s, and the change in threshold voltage before and after bias stress application was 1.4 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. Example 3 Resin 3 (3.8 g, yield 72%) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was changed to 4-(trifluoromethyl)cinnamic acid (Tokyo Chemical Industry Co., Ltd.).

[0170] 1 As a result of analysis by 1 H-NMR, it was confirmed that the obtained resin 3 (formula below) contained 14 mol % and 86 mol % of structural units represented by formula (1) and formula (2), respectively.

[0171] [ka]

[0172] 1 H-NMR (400MHz, CDCl3): δ7.58(brs,-CH=CH-Ph),7.54~6.46(m,aromatic,-CH=CH-Ph),2.08(brs,-CH2-CH-),1.82~1.45(bm,-CH2-) An insulating film was formed using the obtained resin 3 in the same manner as in Example 1, and an organic field-effect transistor device was fabricated. The transfer characteristics were evaluated in the same manner as in Resin 1, and the mobility was found to be 0.32 cm 2 / V·s, and the change in threshold voltage before and after bias stress application was 0.2 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. Example 4 Resin 4 (4.0 g, 80% yield) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with trans-3,5-bis(trifluoromethyl)cinnamic acid (Apollo Scientific) and the amount of trifluoromethanesulfonic acid added was changed to 7.2 g (48 mmol).

[0173] 1 As a result of analysis by 1 H-NMR, it was confirmed that the resulting resin 4 (formula below) contained 22 mol % and 78 mol % of structural units represented by formula (1) and formula (2), respectively.

[0174] [ka]

[0175] 1 H-NMR (400MHz, CDCl3): δ7.63(brs,-CH=CH-C(O)-),8.00~6.48(m,aromatic,-CH=CH-Ph),2.05(brs, -CH2-CH-),1.73~1.42(bm,-CH2-) An insulating film was formed using the obtained resin 4 in the same manner as in Example 1, except that the solution concentration was changed to 12 wt %, and an organic field-effect transistor device was fabricated. The transfer characteristics were evaluated in the same manner as in Resin 1, and the mobility was found to be 0.32 cm 2 / V·s, and the change in threshold voltage before and after bias stress application was 0.2 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. Example 5 Resin 5 (3.0 g, yield 53%) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with 2,3,4,5,6-pentafluorocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0176] 1 As a result of analysis by 1 H-NMR, it was confirmed that the resulting resin 5 (formula below) contained 13 mol % and 87 mol % of structural units represented by formula (1) and formula (2), respectively.

[0177] [ka]

[0178] 1 H-NMR (400MHz, CDCl3): δ7.73(brs,-CH=CH-C(O)-),7.64~6.50(m,aromatic,-CH=CH-Ph),2.01(brs, -CH2-CH-),1.81~1.41(bm,-CH2-) The obtained resin 5 was used and the UV irradiation dose was 200 mJ / cm 2 An insulating film was formed using the same method as in Example 1, except that the resin was changed to 2 / V·s, and the threshold voltage shift was 0.4 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. Example 6 Resin 6 (4.0 g, 80% yield) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with 3-nitrocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0179] 1 As a result of analysis by 1 H-NMR, it was confirmed that the resulting resin 4 (formula below) contained 57 mol % and 43 mol % of structural units represented by formula (1) and formula (2), respectively.

[0180] [ka]

[0181] 1 H-NMR (400MHz, CDCl3): δ7.52(brs,-CH=CH-C(O)-),8.58~6.60(m,aromatic,-CH=CH-Ph),2.15(brs, -CH2-CH-),1.90~1.48(bm,-CH2-) An insulating film was formed using the obtained resin 6 in the same manner as in Example 1, and an organic field-effect transistor device was fabricated. The transfer characteristics were evaluated in the same manner as in Resin 1, and the mobility was found to be 0.35 cm 2 / V·s, and the threshold voltage shift was 1.6 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. Example 7 Resin 7 (3.7 g, 82% yield) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with 3-fluorocinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0182] 1 As a result of analysis by 1 H-NMR, it was confirmed that the resulting resin 7 (formula below) contained 23 mol % and 77 mol % of structural units represented by formula (1) and formula (2), respectively.

[0183] [ka]

[0184] 1 H-NMR (400MHz, CDCl3): δ7.60(brs,-CH=CH-C(O)-),7.45~6.50(m,aromatic,-CH=CH-Ph),2.05(brs, -CH2-CH-),1.82~1.45(bm,-CH2-) An insulating film was formed using the obtained resin 7 in the same manner as in Example 1, and an organic field-effect transistor device was fabricated. The transfer characteristics were evaluated in the same manner as in Resin 1, and the mobility was found to be 0.21 cm 2 / V·s, and the threshold voltage shift was 1.8 V, demonstrating excellent mobility and bias stress resistance. The evaluation results are also shown in Table 1. (Comparative Example 1) 6.4 g (38.4 mmol) of cinnamic acid chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.0 g of polystyrene (DIC, Ltd.) with a weight-average molecular weight of 55,000 were weighed into a 200 mL Schlenk flask in a glove box. After removing the flask from the glove box, 29 mL of dichloromethane was added and dissolved at room temperature with stirring. While stirring, 5.8 g (38.4 mmol) of trifluoromethanesulfonic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added dropwise using a syringe. As the polymer solution was added, it turned reddish-purple. After the addition, the mixture was allowed to react at room temperature for 4 hours. The solution after the reaction was cannulated into a saturated aqueous solution of sodium bicarbonate to neutralize the trifluoromethanesulfonic acid and hydrochloric acid in the system. The aqueous layer of the neutralized solution was removed by decantation, and the dichloromethane layer was separated. Water was added again, and the aqueous layer was removed by decantation. This procedure was repeated twice to remove excess sodium bicarbonate. The decanted solution was reprecipitated with 430 mL of methanol, and the polymer was isolated by filtration twice. After drying under reduced pressure at 50°C, 3.7 g (91% yield) of Resin 8 was obtained.

[0185] 1 As a result of analysis by 1 H-NMR, it was confirmed that the obtained resin 1 (formula below) contained 17 mol % and 83 mol % of structural units represented by formula (1) and formula (2), respectively.

[0186] [ka]

[0187] 1 H-NMR (400MHz, CDCl3): δ7.62(brs,-CH=CH-C(O)-),7.39~6.51(m,aromatic,-CH=CH-Ph),2.04(brs, -CH2-CH-),1.78~1.40(bm,-CH2-) An insulating film was formed using the obtained resin in the same manner as in Example 1, and an organic field-effect transistor device was fabricated. The transfer characteristics were evaluated in the same manner as in Resin 1, and the mobility was found to be 0.10 cm 2 / V·s, and the change in threshold voltage was 5.5 V, confirming that both the mobility and bias stress resistance were inferior compared to Examples 1 to 7. The configuration and evaluation results of the fabricated organic field-effect transistor device are also shown in Table 1. (Comparative Example 2) Resin 6 (4.0 g, yield 70%) was obtained in the same manner as in Example 1, except that 3-(trifluoromethyl)cinnamic acid was replaced with 4-methylcinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0188] 1 As a result of analysis by 1 H-NMR, it was confirmed that the obtained resin 4 (formula below) contained 6 mol % and 94 mol % of structural units represented by formula (1) and formula (2), respectively.

[0189] [ka]

[0190] 1 H-NMR (400MHz, CDCl3): δ6.97(brs,-CH=CH-C(O)-),7.75~6.43(m,aromatic,-CH=CH-Ph),1.38(brs, -CH2-CH-),2.38(brs,-CH3) The resulting resin was exposed to UV light at a dose of 1000 mJ / cm 2 An insulating film was formed using the same method as in Example 1, except that the resin was changed to 2 / V·s, and the change in threshold voltage was 4.0 V, confirming that both the mobility and bias stress resistance were inferior compared to Examples 1 to 7. The configuration and evaluation results of the fabricated organic field-effect transistor device are also shown in Table 1.

[0191] In Examples 1 to 7, in which organic field-effect transistors were formed using a resin in which the HOMO level of the repeating unit represented by formula (2) was −6.4 eV or less, the mobility was higher and the bias stress resistance was better than in Examples 1 and 2, in which organic field-effect transistors were formed using a resin in which the HOMO level of the repeating unit represented by formula (2) was higher than −6.4 eV. [Industrial Applicability]

[0192] It is possible to provide a resin suitable for high-quality organic field-effect transistor devices that can be manufactured using printed electronics technology.< / nmr>

Claims

1. A resin containing repeating units represented by formula (1) and formula (2), wherein the repeating units represented by formula (2) have a HOMO level of −6.4 eV or less, and the resin contains 20 mol % or more of the repeating units of formula (2) relative to the total number of the repeating units of formula (1) and formula (2). 【Chemistry 1】 （１） (In formula (1), R 1 represents hydrogen, S １ represents -O- or -C(O)-, p represents 0, A １ represents a phenyl group, a naphthyl group, an anthryl group, or a biphenyl group, and Y represents a halogen, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1 to C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group. Also, k represents 0. Here, s represents A １ represents the number of carbon atoms that make up the 【Chemistry 2】 （２） {(In formula (2), R 2a represents hydrogen, S ２ represents -O- or -C(O)-, q represents 0, A ２ represents a phenyl group, a naphthyl group, an anthryl group, or a biphenyl group, Y represents a substituent defined in formula (1), j represents an integer of 0, and m represents an integer of 1 to (rj-1). ２ represents the number of carbon atoms constituting the group; and Z represents the organic group of formula (A). 【Transformation 3】 (A) (In formula (A), R 2 and R 3 represent hydrogen, and R ４ R to R8 each independently represent hydrogen, halogen, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, C1 to C18 alkyl group, fluoroalkyl group, or cycloalkyl group, and have at least one halogen, cyano group, nitro group, carboxyalkyl group, or fluoroalkyl group.

2. An insulating film comprising a crosslinked product of the resin according to claim 1.

3. An organic field-effect transistor device in which an organic semiconductor layer provided with a source electrode and a drain electrode and a gate electrode are laminated on a substrate with a gate insulating layer interposed therebetween, wherein the gate insulating layer is the insulating film according to claim 2.

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