WO2018168676A1

WO2018168676A1 - Photocrosslinkable polymer, insulating film, planarization film, lyophilic/liquid repellent patterned film, and organic field effect transistor device comprising same

Info

Publication number: WO2018168676A1
Application number: PCT/JP2018/009167
Authority: WO
Inventors: 山川浩; 奥慎也; 弓野翔平; 李廷輝; 片桐史章
Original assignee: 東ソー株式会社
Priority date: 2017-03-16
Filing date: 2018-03-09
Publication date: 2018-09-20

Abstract

Provided is a resin which is excellent in terms of solubility in common solvents, crosslinking temperature, time required for crosslinking, solvent resistance (cracking resistance), dielectric breakdown strength, leakage current, solvent wettability, and planarity in cases where the resin is formed into a thin film. A resin which comprises repeating units represented by formula (1) and formula (2), and wherein the repeating unit represented by formula (2) is contained in an amount of 20% by mole or more relative to the total amount of the repeating units represented by formula (1) and formula (2). (In formula (1), R1 represents a hydrogen atom or a C1-C6 alkyl group; S1 represents -O- or -C(O)-; p represents 0 or 1; A1 represents a C6-C19 aryl group; Y represents a halogen atom, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group or a cycloalkyl group; and k represents an integer of from 0 to (s - 1) wherein s represents the number of carbon atoms constituting the aromatic group A1.) {(In formula (2), R2 represents a hydrogen atom or a C1-C6 alkyl group; S2 represents -O- or -C(O)-; q represents 0 or 1; A2 represents a C6-C19 aryl group; Y represents a substituent as defined in formula (1); j represents an integer of from 0 to (r - 2) and m represents an integer of from 1 to (r - j - 1), wherein r represents the number of carbon atoms constituting the aromatic group A2; and Z represents at least one organic group selected from among formulae (A)-(D).) (In formulae (A)-(D), each of R3 and R4 independently represents a hydrogen atom, a C1-C6 alkyl group, an aryl group or a carboxyalkyl group; and each of R5-R29 independently represents a hydrogen atom, a halogen atom, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group or a cycloalkyl group.)}

Description

Photocrosslinkable polymer, insulating film, planarizing film, hydrophilic / repellent patterning film, and organic field effect transistor device including the same

The present invention forms a film having excellent flatness by coating in a solution state, easily crosslinks by light irradiation for a short time, and has solvent resistance (crack resistance) but also wettability to solvent ( The present invention relates to a resin having excellent overcoat property and high dielectric breakdown strength.

High dielectric breakdown strength, low leakage current, solubility in general-purpose organic solvents, solvent resistance (crack resistance) for the resin used to form polymer dielectric layers (insulating film layers) used in organic field effect transistor devices ) Is required, and the polymer dielectric layer after crosslinking is required to have excellent wettability and high flatness with respect to an organic solvent.

Dielectric breakdown strength refers to the maximum electric field value that can be applied without destroying the dielectric layer that constitutes the device. The higher the dielectric breakdown strength, the higher the stability of the device. The leakage current is an index indicating the magnitude of a current other than the original conductive path, for example, a current flowing from the gate electrode through the insulating dielectric layer to the source electrode. The leakage current is obtained by preparing a MIM capacitor having a three-layer structure of metal / dielectric / metal and measuring the value of current flowing in the dielectric layer.

While solubility in general-purpose solvents is an essential requirement for producing organic field effect transistor devices by printing methods, in organic field effect transistor devices, a polymer dielectric layer is an overlay layer such as an organic semiconductor layer. Laminated. Therefore, when an overlay layer is formed on a polymer dielectric layer by a printing method using a solvent, the polymer dielectric must not be dissolved in this solvent (a solvent used in the printing method). . Therefore, the polymer dielectric layer (insulating film layer) must be dissolved in a general-purpose organic solvent when forming the layer, and insoluble in the organic solvent after forming the layer. Conflicting performance is required.

As a technique for meeting such demands, a technique for crosslinking a polymer dielectric layer formed by solution film formation is known. For example, benzocyclobutene resin and polyvinyl phenol resin are known. However, when a benzocyclobutene resin has a high crosslinking temperature of 250 ° C. and a plastic is used as a base material, the base material is thermally deformed. It was difficult and the curing time was long and the economy was poor. Furthermore, it is extremely difficult to apply to the roll-to-roll process, and the flatness of the film that affects the device performance is not sufficient. Polyvinylphenol uses a melamine resin or the like as a cross-linking agent and requires a long curing reaction at a temperature of about 150 ° C., and is extremely difficult to apply to a roll-to-roll process. In addition, the hydroxyl groups of the polyvinylphenol resin do not disappear completely, and there is a problem of high leakage current estimated to be caused by hydrophilicity due to the remaining hydroxyl groups. Furthermore, the flatness of the film was not sufficient.

Also, the use of a fluorine-based cyclic ether resin, polyparaxylylene resin, or the like as a type of resin that does not require crosslinking used for the polymer dielectric layer (insulating film layer) has been proposed. Since the fluorine-based cyclic ether resin does not dissolve in a general-purpose organic solvent after film formation, it has an advantage that it is insoluble in a general-purpose solvent even if it is not crosslinked, but is inferior in economic efficiency. Furthermore, since this material has a low surface tension, the wettability with respect to the base material is poor, and the base material that can be coated or printed has a great restriction. In addition, since the wettability is poor, there is a problem that a pinhole is easily formed and a leakage current is high. Polyparaxylylene resin has the advantage that it is not dissolved in a general-purpose solvent because it is deposited on a substrate by vapor deposition and polymerized on the substrate by vacuum deposition. It has a fatal defect that it cannot respond.

Photocrosslinking technology is known as a means that can be crosslinked at a low temperature and shortens the crosslinking time. For example, it has photocrosslinkability such as cinnamoyl group for polymers having hydroxyl groups in the side chain such as poly (hydroxyethyl methacrylate), vinylphenol-methyl methacrylate copolymer, polyacetoxyethyl methacrylate, polyhydroxyethyl methacrylate, etc. A technique of using a photocrosslinkable polymer obtained by reacting a compound having a polymer dielectric as a polymer dielectric is disclosed (for example, see Patent Document 1). In addition, a photocrosslinkable polymer in which coumarin is introduced as a photocrosslinkable group into a vinyl polymer having a phenol group in the side chain has been proposed (see, for example, Patent Document 2). However, in any of the techniques disclosed in Patent Document 1 and Patent Document 2, it is difficult to react all the hydroxyl groups present in the hydroxyl group-containing polymer with the photocrosslinkable compound, and the remaining hydroxyl groups are unavoidable. . As a result, when these polymers are used as insulating films, the leakage current value and / or the hysteresis increase. Patent Document 1 also discloses a technique for reducing the amount of residual hydroxyl groups by reacting unreacted hydroxyl groups with trifluoroacetic anhydride for esterification. However, it is extremely difficult to completely eliminate the hydroxyl group, and there is a problem that the wettability with respect to the organic solvent is lowered by the introduction of the fluorine compound.

In addition, a technique using poly (vinyl cinnamate) as a polymer dielectric layer of an organic field effect transistor device has been proposed (see, for example, Non-Patent Document 1 and Non-Patent Document 2), but the solution was applied. The flatness of the polymer dielectric layer (insulating film layer) is about 0.7 nm, and further flattening has been demanded.

In addition to these, technologies relating to photosensitive resins are known. For example, a compound having a photoreactive group is introduced into an aromatic vinyl polymer such as polystyrene or poly-α-methylstyrene by Friedel-Crafts acylation reaction. A technique related to the photosensitive resin is disclosed in the 1950s. However, this technique has a problem that the resin gels during the manufacturing process if a large number of photoreactive groups are introduced to shorten the exposure time. Therefore, the introduction amount of the photoreactive group needs to be less than 17 mol% with respect to the total number of moles of monomers constituting the polymer (for example, see Patent Document 3 and Patent Document 4). Therefore, when the photosensitive resin that reacts (crosslinks) by light irradiation is used as the above-described polymer dielectric layer, the concentration of the photoreactive group is small, and thus the crosslink density of the photocrosslinked film is low. As a result, when an organic solvent solution of an organic semiconductor or a polymer solution is printed on the film, the crosslinked film absorbs the solvent and swells. When this film was dried, the film contracted again, and there was a problem that cracks occurred in the film during the contraction process. Further, since the concentration of the photoreactive group is low, there is a problem that the crosslinking time is long and the productivity is low.

As described above, conventionally used resins for polymer dielectric layers (insulating film layers) are soluble in general-purpose solvents, crosslinking temperature, time required for crosslinking, solvent resistance (crack resistance), solvent resistance There are some problems with respect to wettability, leakage current, dielectric breakdown strength, and flatness when formed into a film. A resin capable of solving all these problems and a polymer dielectric layer (insulating film layer) containing the resin It was sought after.

Japanese Patent No. 5148624 Japanese Patent No. 5960202 US Pat. No. 2,662,302 U.S. Pat. No. 2,708,665

The present invention has been made in view of the above problems, and its purpose is solubility in general-purpose solvents, crosslinking temperature, time required for crosslinking, solvent resistance (crack resistance), wettability to solvents, leakage current, An object of the present invention is to provide a resin capable of producing a polymer dielectric layer (insulating film layer) having excellent performance in terms of dielectric breakdown strength.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific resin is soluble in a general-purpose solvent required for an insulating film, a crosslinking temperature, a time required for crosslinking, and solvent resistance (crack resistance). As a result, the present invention has been completed by finding that it has excellent wettability to solvent, leakage current, and dielectric breakdown strength.

That is, the present invention resides in the following [1] to [5].
[1] A resin containing repeating units represented by formula (1) and formula (2), wherein the repeating unit of formula (2) is added to the total number of repeating units of formula (1) and formula (2). Resin containing 20 mol% or more.

(In the formula (1), R ₁ represents hydrogen or a C1-C6 alkyl group, S ₁ represents —O— or —C (O) —, p represents 0 or 1, and A ₁ represents a C6-C19 aryl. Y represents a halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group, and k represents 0 to (s-1 Where s represents the number of carbon atoms constituting A _1. )

{(In the formula (2), R ₂ represents hydrogen or a C1-C6 alkyl group, S ₂ represents —O— or —C (O) —, q represents 0 or 1, and A ₂ represents C6 to C19. Y represents an 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), where r Represents the number of carbon atoms constituting A _2. Z represents at least one organic group selected from formulas (A) to (D).

(In the formulas (A) to (D), R ₃ and R ₄ each independently represent hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group, and R ₅ to R ₂₉ each independently represent Represents hydrogen, halogen, cyano group, carboxyalkyl group, alkyl ether group, aryl ether group, C1-C18 alkyl group, fluoroalkyl group, or cycloalkyl group)}
[2] An insulating film comprising the cross-linked product of the resin according to [1].
[3] In the 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 stacked on a substrate via a gate insulating layer, the gate insulating layer is described in [2] above. An organic field effect transistor device characterized by being an insulating film.
[4] A planarization film comprising the resin according to [1] and / or the crosslinked product of the resin according to [1].
[5] A hydrophilic / repellent patterning film comprising the resin according to [1] and / or a crosslinked product of the resin according to [1].

The present invention will be described in detail below.

The resin of the present invention contains repeating units of the above formula (1) and the above formula (2).

In the formula (1), R ₁ represents hydrogen or a C1-C6 alkyl group.

The C1-C6 alkyl group for R ₁ in the 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.

In the formula (1), S ₁ represents —O— or —C (O) —.

In the formula (1), p represents 0 or 1.

In the formula (1), A ₁ represents a C6 to C19 aryl group.

The C6 to C19 aryl group in A ₁ in the formula (1) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

In the formula (1), Y represents a halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group.

There is no restriction | limiting in particular as a halogen in Y in Formula (1), For example, chlorine, a fluorine, etc. are mentioned.

There is no restriction | limiting in particular as a carboxyalkyl group in Y in Formula (1), For example, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group etc. are mentioned.

The alkyl ether group for Y in the 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.

The aryl ether group in Y in the formula (1) is not particularly limited, and examples thereof include a phenoxy group, 4-methylphenoxy group, 4-tert-butylphenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like. .

The C1-C18 alkyl group for Y in the 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.

The fluoroalkyl group for Y in formula (1) is not particularly limited, and examples thereof include 1,1,1-trifluoroethyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1,1, Examples include 1,2,2,3,3-heptafluorobutyl group.

The cycloalkyl group for Y in the formula (1) is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. In the formula (1), k is an integer of 0 to (s-1). To express. Here, s represents the number of carbon atoms constituting the A _1.

In the formula (2), R ₂ represents hydrogen or a C1-C6 alkyl group.

The C1-C6 alkyl group in R ₂ in the 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.

In the formula (2), S ₂ represents —O— or —C (O) —.

In the formula (2), q represents 0 or 1.

In the formula (2), A ₂ represents a C6 to C19 aryl group.

The C6 to C19 aryl group in A ₂ in Formula (2) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

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

In the formula (2), m represents an integer of 1 to (r−j−1). Here, r represents the number of carbon atoms constituting A ₂ , and j represents an integer of 0 to (r−2).

In formula (2), Z represents at least one organic group selected from formulas (A) to (D).

In formulas (A) to (D), R ₃ and R ₄ each independently represent hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group, and R ₅ to R ₂₉ each independently It represents hydrogen, halogen, cyano group, carboxyalkyl group, alkyl ether group, aryl ether group, C1-C18 alkyl group, fluoroalkyl group, or cycloalkyl group.

The C1-C6 alkyl group in R ₃ and R ₄ in the 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. Etc.

The aryl group in R ₃ and R ₄ in the formulas (A) to (D) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

The carboxyalkyl group for R ₃ and R ₄ in formulas (A) to (D) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.

The halogen in R ₅ to R ₂₉ in the formulas (A) to (D) is not particularly limited, and examples thereof include chlorine and fluorine.

The carboxyalkyl group in R ₅ to R ₂₉ in the formulas (A) to (D) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.

The alkyl ether group in R ₅ to R ₂₉ in the formulas (A) to (D) 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. .

The aryl ether group in R ₅ to R ₂₉ in the formulas (A) to (D) is not particularly limited, and examples thereof include a phenoxy group, a p-methylphenoxy group, a p-ethylphenoxy group, and a p-methoxyphenoxy group. Is mentioned.

The alkyl group of C1 to C18 in R ₅ to R ₂₉ in the 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. N-hexyl group, n-decyl group, n-octadecyl group and the like.

The fluoroalkyl group for R ₅ to R ₂₉ in the formulas (A) to (D) is not particularly limited, and examples thereof include 1,1,1-trifluoroethyl group, 1,1,1,2,2- Examples thereof include a pentafluoropropyl group and a 1,1,1,2,2,3,3-heptafluorobutyl group.

The cycloalkyl group in R ₅ to R ₂₉ in the formulas (A) to (D) is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

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

Specific examples of the organic group represented by the formula (B) include the following.

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

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

The polymer containing the repeating unit of the specific formula (1) and formula (2) used in the present invention contains an aromatic group and contains a hydroxyl group, an amino group, a thiol group and the like that react with an acid chloride. If not, it can be used without any restrictions.

In the present invention, there is no limitation on the molecular weight of the resin having the repeating unit of the above formula (1) and the above formula (2), for example, those having 200 to 10,000,000 (g / mol). Can be used. From the viewpoint of the solution viscosity and mechanical strength of the obtained resin, it is preferably 10,000 to 1,000,000 (g / mol).

The resin having repeating units of the above formulas (1) and (2) used in the present invention can be obtained by introducing a photocyclizable compound into an aromatic group-containing polymer by Friedel-Crafts acylation reaction. Here, in the present invention, the photocyclization compound is introduced into a film in a certain amount or more, so that the film has excellent flatness and can be photocrosslinked in a short time. It is inferior in flatness only and cannot be photocrosslinked.

In the present invention, the photocyclizable compound is represented by the cinnamic acid chloride compound represented by the following formula (3), the phenylethenylbenzoic acid chloride compound represented by the following formula (4), and the following formula (5). Pyridinylethenylbenzoic acid chloride and coumarin-6-carboxylic acid chloride represented by the following formula (6) are shown. Of these, cinnamic acid chloride, which is easy to produce, is preferably used. Moreover, these compounds can also use 2 or more types together as needed.

(In formulas (3) to (6), R ₃ to R ₂₉ are the same as defined in formulas (A) to (D).)
The amount of the above-mentioned acid chloride charged in the resin having the repeating unit of the formula (1) and the formula (2) is the aromatic contained in the resin in order to improve the solubility of the resulting resin in the organic solvent and the storage stability. The amount is preferably 0.2 to 2.0 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the group. The amount of photoreactive groups introduced into the aromatic group in the reaction is the solubility in organic solvents, storage stability, ease of photocrosslinking, and solvent resistance (crack resistance) of the resin layer after photocrosslinking. From this point of view, the amount is preferably 0.2 to 1.0 mol, more preferably 0.2 to 0.7 mol with respect to 1 mol of the aromatic group contained in the resin.

The aromatic group-containing polymer into which the photoreactive group is introduced by Friedel-Crafts acylation reaction is not limited as long as it is inactive with respect to the reaction catalyst described later. For example, poly-α-methylstyrene Polystyrene, such as poly-p-methoxystyrene and syndiopolystyrene; polyvinyl naphthalene; polyvinyl biphenyl; polyvinyl anthracene; polyvinyl carbazole; polyvinyl aryl ketone such as polyvinyl phenyl ketone; styrene butadiene copolymer; ethylene / styrene copolymer;・ Acrylonitrile copolymer; Styrene / alkyl acrylate copolymer; Styrene / alkyl methacrylate copolymer; Styrene / α-phenylalkyl acrylate copolymer; Styrene / maleic anhydride copolymer; Styrene / acrylic Sulfuric acid copolymer; Styrene / 4-vinylpyridine copolymer; Styrene / trans-1,3-pentadiene copolymer; Styrene / 2,4,6-trimethylstyrene copolymer; Styrene / p-acetoxystyrene copolymer Styrene / vinyl-tris (trimethoxysiloxy) silane copolymer; Styrene / vinyl benzoate copolymer; Styrene / vinyl butyl ether copolymer; Poly (styrene / ethylene / butylene) copolymer; Poly (styrene / polymer) Ethylene / propylene) copolymer; poly (styrene / ethylene / propylene / butylene) copolymer; poly (propylene / styrene) copolymer; polystyrene-b-poly (ethylene / propylene) -b-polystyrene copolymer; Polystyrene-b-poly (ethylene / butylene) -b-polystyrene copolymer Polystyrene-b-poly (ethylene / propylene / butylene) -b-polystyrene copolymer; diblock copolymer, multiblock copolymer, star polymer, dendrimer, graft copolymer of polystyrene and polyisoprene Hydrogenated products: Diblock copolymers, multiblock copolymers, star polymers, dendrimers, and graft copolymers made of polystyrene and polybutadiene; polystyrene-b-polyisobutylene-b-polystyrene copolymers; polystyrene And polyisobutylene multiblock copolymers, star polymers and dendrimers; polyvinyl naphthalene and polybutadiene or polyisoprene diblock copolymers, multiblock copolymers, star polymers, dendrimers and graft copolymers Hydrogenated polymer; diblock copolymer consisting of polyvinyl naphthalene and polyisobutene, multiblock copolymer, star polymer, dendrimer, graft copolymer; diblock copolymer consisting of polyvinyl anthracene and polybutadiene or polyisoprene, Hydrogenated polyblock copolymer, star polymer, dendrimer, graft copolymer; diblock copolymer consisting of polyvinyl anthracene and polyisobutene, multiblock copolymer, star polymer, dendrimer, graft copolymer; polyvinyl biphenyl Diblock copolymer, multiblock copolymer, star polymer, dendrimer, graft copolymer hydrogenated product of polybutadiene or polyisoprene; polyvinyl biphenyl and polyisobutene Diblock copolymer, multiblock copolymer, star polymer, dendrimer, graft copolymer; diblock copolymer consisting of poly (styrene-co-vinylnaphthalene) and polyisoprene or polybutadiene, multiblock copolymer , Star polymers, dendrimers, graft copolymers, and hydrogenated products thereof; diblock copolymers composed of poly (styrene-co-vinylnaphthalene) and polyisobutene, multiblock copolymers, star polymers, dendrimers, graft copolymers Diblock copolymer, multiblock copolymer, star polymer, dendrimer, graft copolymer, and hydrogenated product thereof comprising poly (styrene-co-vinylanthracene) and polyisoprene or polybutadiene; poly (styrene- co-bini Diblock copolymer consisting of luanthracene) and polyisobutene, multiblock copolymer, star polymer, dendrimer, graft copolymer; diblock copolymer consisting of poly (styrene-co-vinylbiphenyl) and polyisoprene or polybutadiene , Multiblock copolymers, star polymers, dendrimers, graft copolymers, and hydrogenated products thereof; diblock copolymers composed of poly (styrene-co-vinylbiphenyl) and polyisobutene, multiblock copolymers, star polymers , Dendrimer, graft copolymer; petroleum resin, etc. are exemplified, but in order to reduce the leakage current by lowering the dielectric constant, a polymer composed only of an aromatic hydrocarbon and an aliphatic hydrocarbon is used. Is preferred. Moreover, these copolymers can also be used in combination of 2 or more types.

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

In the present invention, a known super strong acid can be used as a reaction catalyst, and there is no limitation as long as it is a super strong acid, and examples thereof include trifluoromethane sulfonic acid, fluorosulfonic acid, fluoroantimonic acid, and carborane acid. The addition amount of the catalyst is 0.1 to 1.5 times mol of the above acid chloride in order to avoid complicated neutralization after the reaction and to prevent the reaction rate from decreasing. Is preferred.

The Friedel-Crafts acylation reaction is an exothermic reaction and may cause a side reaction in which the photoreactive group is crosslinked by heating in this reaction system. Therefore, in the present invention, in order to suppress the side reaction, it is preferable to carry out by a solution reaction in which the reaction temperature can be easily controlled. The reaction solvent used in the solution reaction in the present invention can be used without any limitation as long as it is stable against the Friedel-Crafts reaction, and is sufficiently dehydrated chlorine-based hydrocarbon solvent, aliphatic carbonization which is inert to the reaction. A hydrogen solvent, a sulfur-containing solvent, a nitrile solvent or the like is preferably used. Examples of chlorinated hydrocarbon solvents include methylene chloride, carbon tetrachloride, 1,1,2-trichloroethane, chloroform, etc., aliphatic hydrocarbon solvents such as cyclohexane, and sulfur-containing solvents such as carbon disulfide and sulfonedimethyl. Examples thereof include sulfoxide, dimethyl sulfate and dimethyl sulfone, and examples of the nitrile solvent include acetonitrile.

In the Friedel-Crafts acylation reaction, the reaction temperature is not particularly limited, but it is preferably 0 to 40 ° C. from the viewpoint of economy related to cooling and heating, and 0 to 15 ° C. from the viewpoint of suppressing the formation of microgel. Further preferred. Moreover, although it is possible to carry out at the reflux temperature of the solvent used as necessary, a temperature of less than 200 ° C. is preferred.

In the Friedel-Crafts acylation reaction, the reaction time is not particularly limited, and examples thereof include 5 to 100 hours. From the viewpoint of reaction rate and economy, it is preferably 10 hours to 50 hours.

In addition, the resin having the repeating unit of formula (1) and formula (2) may contain a structure based on the cyclization of the photoreactive group in the polymer molecule as long as the solubility is not impaired.

Examples of the structure based on cyclization of the photoreactive group include structures represented by the following formulas (7) to (10).

(In formulas (7) and (8), R ₃ to R ₉ are the same as in formula (3))

(In Formula (9) and Formula (10), R ₃ , R ₄ and R ₁₀ to R ₁₈ are the same as in Formula (4)).

(In Formula (11) and Formula (12), R ₃ , R ₄ and R ₁₉ to R ₂₆ are the same as in Formula (5)).

(In Formula (13) and Formula (14), R ₃ , R ₄ , R ₂₇ to R ₂₉ are the same as in Formula (6))
In addition, the resin having the repeating units of the formulas (1) and (2) may contain, for example, a dimerized photoreactive group as shown below.

(In Formula (15), Formula (16), and Formula (17), R ₃ and R ₄ to R ₂₆ are the same as those defined in Formulas (A) to (C). A, b, and c) Represents an integer of 0 to 4, R _A is a substituents selected from R ₅ to R ₉ defined in Formula (A), and R _B is selected from R ₁₄ to R ₁₈ defined in Formula (B) B substituents, R _C represents c substituents selected from R ₂₃ to R ₂₆ defined in formula (C).)
In the present invention, when Z in the formula (2) is an organic group represented by the formula (A), the resins having repeating units of the formula (1) and the formula (2) are represented by the formulas (1) and (1). The resin may have a repeating unit (2) and further have a repeating unit represented by the formula (18). At this time, since a part of the repeating unit of the formula (2) becomes the repeating unit of the formula (18), generation of microgel can be suppressed, and the resin is more excellent in productivity.

(In the formula (18), R ₂ , S ₂ , A ₂ and Y are the substituents defined in the formula (2), q is an integer defined in the formula (2), and n is 0 to (t-4) Here, t represents the total number of carbon atoms constituting A _2. Also, d and e are located at positions ortho to each other on the aromatic group A ₂ (bonded to adjacent carbon atoms). ) Represents a single bond, and R ₃ to R ₉ are the same as defined in formula (A).
In formula (18), n represents an integer of 0 to (t-4). Here, t represents the total number of carbon atoms constituting the A _2. D and e each represent a single bond located at the position of the ortho position on the aromatic group A ₂ (bonded to adjacent carbon).

Further, the resin having the repeating unit of the formula (1) and the formula (2) has the repeating unit of the above formula (1) and the above formula (2), and further has the repeating unit represented by the formula (19). Resin may be used. At this time, the liquid repellency in the case of the hydrophilic / repellent patterning film is improved, and the resin becomes more excellent in resolution when the fine electrode is formed.

(In the formula (19), A ₃ is a C6-C19 aryl group, Y is a substituent defined in the formula (1), R ₃₀ is hydrogen or a C1-C6 alkyl group, and R _f is a C1-C18 the fluoroalkyl group, v is an integer of 0 ~ (u-2), w represents an integer of 1 ~ (u-v-1 ). here, u represents the number of carbon atoms constituting the _{a 3.} )
In the formula (19), A ₃ represents a C6 to C19 aryl group.

The C6 to C19 aryl group in A ₃ in Formula (19) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

In formula (19), Y represents an organic group similar to the organic group defined in formula (1).

In the formula (19), R ₃₀ represents hydrogen or a C1-C6 alkyl group.

The C1-C6 alkyl group for R ₃₀ in formula (19) 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.

In the formula (19), R _f represents a C1-C18 fluoroalkyl group.

The C1-C18 fluoroalkyl group in R _f in the formula (19) is not particularly limited, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, Perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluorododecyl group, perfluorooctadecyl group and other linear perfluoroalkyl groups; perfluoroisopropyl group, perfluoro Branched perfluoroalkyl groups such as fluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, perfluoroneopentyl group; perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopenty Cyclic perfluoroalkyl groups such as thiol groups and perfluorocyclohexyl groups; 1,1,1-perfluoroethyl groups, 1,1,1,2,2-pentafluoropropyl groups, 1,1,1,2,2 , 3,3-heptafluorobutyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group and the like partially fluorinated semifluoroalkyl groups.

In the formula (19), v represents an integer of 0 to (u-2), and m represents an integer of 1 to (uv-1). Here, u represents the number of carbon atoms constituting the A _3.

It can be coated or printed on various substrates using a solution obtained by dissolving a resin having repeating units of the above formulas (1) and (2) in a solvent.

As the solvent, any solvent that dissolves the resin can be used without any limitation. For example, cyclohexane, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, n-hexylbenzene, tetralin, decalin, isopropylbenzene, chlorobenzene. Aromatic hydrocarbons such as: 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 and cyclohexanone; Ethyl acetate and dimethyl Examples include ester compounds such as phthalate, methyl salicylate, and amyl acetate; alcohols such as n-butanol, ethanol, and iso-butanol; and 1-nitropropane, carbon disulfide, and limonene. These solvents can be used as a mixture as required.

Examples of the resin according to the present invention 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. , Screen printing, ink jet printing, letterpress reversal printing, and the like. Note that since the insulating film of the present invention is formed using these methods, the insulating film of the present invention is required to have excellent solubility in general-purpose solvents.

When the resin according to the present invention is used as an insulating film, it can be used in a state where the film is formed or as a cross-linked product that is photo-crosslinked (photocyclized) as necessary. In the present invention, when the film is formed and then used as an insulating film without photocrosslinking, the general-purpose solvent used for forming the film exhibits good solubility, and the upper portion of the film In addition, it is necessary that the organic semiconductor layer can be formed using a solvent different from the general-purpose solvent. At this time, when the film has solvent resistance (crack resistance) with respect to the organic semiconductor solution, it can be used as an insulating film with the film formed. In addition, when it is not excellent in solvent resistance (crack resistance), film formation by a printing method cannot be performed, and it is necessary to form into a film by methods, such as a vapor deposition method inferior to the printing method.

When the resin according to the present invention is used as an insulating film, radiation is used for photocrosslinking (photocyclization), for example, ultraviolet rays having a wavelength of 245 to 350 nm are exemplified. The irradiation amount is appropriately changed depending on the composition of the resin. For example, 150 to 3000 mJ / cm ² can be mentioned, and it is preferable to prevent a decrease in the degree of crosslinking and to improve economy by shortening the process. 50 to 1000 mJ / cm ² . Irradiation with ultraviolet rays is usually carried out in the atmosphere, but it can also be carried out in an inert gas or in a certain amount of inert gas flow as necessary. If necessary, a photosensitizer can be added to promote the photocrosslinking reaction. The photosensitizer used is not particularly limited, and examples thereof include benzophenone compounds, anthracene compounds, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds, etc., but benzophenone compounds having high compatibility with the resin used in the present invention. Is preferred. The sensitizers can be used in combination of two or more as required.

The resin of the present invention can be crosslinked by ultraviolet rays, but may be heated if necessary. The temperature in the case of heating in addition to the ultraviolet irradiation is not particularly limited, but a temperature of 120 ° C. or lower is preferable in order to avoid thermal deformation of the resin used.

Further, the resin of the present invention can be crosslinked efficiently in a short time, and the time required for crosslinking can be within 5 minutes. Note that, since it is suitable for controlling the crosslinking time, the time required for crosslinking is preferably within 1 to 2 minutes.

The resin of the present invention can be formed into a film and used as a gate insulating layer (polymer dielectric layer) in an organic field effect transistor (OFET). The organic field effect transistor 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 a gate insulating layer (polymer dielectric layer). .

The insulating film obtained from the resin of the present invention has a low leakage current because the formation of fine holes (pinholes) that cause leakage is suppressed. Further, when the insulating film is used as a polymer dielectric layer, the leakage current is preferably 0.01 nA or less from the viewpoint of practicality as an organic field effect transistor (OFET) element.

The insulating film obtained from the resin of the present invention has excellent wettability with respect to a solvent. When used as a gate insulating layer (polymer dielectric layer), the bottom gate / bottom contact (BGBC) type and the top gate / bottom contact are used. In a (TGBC) type organic field effect transistor device, when an appropriate amount of an organic semiconductor solution covering the S (source) electrode and D (drain) electrode on the layer is applied, the entire electrode can be covered. .

The insulating film obtained from the resin of the present invention has excellent flatness. When used as a gate insulating layer (polymer dielectric layer), the surface roughness (Ra) is 0. 0 from the viewpoint of flatness. It is preferable that it is 5 nm or less.

When an insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), the threshold voltage of the FET element is 0 from the viewpoint of practicality as an organic field effect transistor (OFET) element. It is preferably 2.0 V or less, or −2.0 V or more and less than 0 V.

When the insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), the mobility of the FET element is 0. 0 from the viewpoint of practicality as an organic field effect transistor (OFET) element. It is preferably 20 cm ² / Vs or more.

When the insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), from the viewpoint of practicality as an organic field effect transistor (OFET) element, the on-current / off-current of the FET element The ratio is preferably 10 ⁶ or more.

When the insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), from the viewpoint of practicality as an organic field effect transistor (OFET) element, the source-drain current of the FET element It is preferable that there is no hysteresis.

When the insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), the dielectric breakdown strength of the FET element is 4 MV from the viewpoint of practicality as an organic field effect transistor (OFET) element. / Cm or more is preferable.

In the present invention, the organic field effect transistor (OFET) is a bottom gate / bottom contact (BGBC) type, a bottom gate / top contact (BGTC) type, a top gate / bottom contact (TGBC) type, a top gate / top contact (TGTC). Any of the molds may be used. Here, among these organic field-effect transistors having various structures, for example, the structure of a bottom gate / bottom contact (BGBC) type element is shown in FIG.

The resin of the present invention is suitably used as a planarizing film containing the resin of the present invention and / or a cross-linked product of the resin of the present invention, and is particularly suitably used as an insulating planarizing film capable of continuous printing. Here, the planarizing film is a film made of an insulating resin that is applied on the base material and used for the purpose of reducing the surface roughness of the base material itself.

The planarizing film obtained from the resin of the present invention can be continuously printed by dissolving in the above-mentioned organic solvent, has excellent insulating properties and flatness, and can be particularly suitably used as a repellent patterning film. Here, the hydrophilic / repellent patterning is a technique of patterning by hydrophilicizing the surface of a plastic using vacuum ultraviolet (VUV), and a film having a surface patterned by using the technique is called a hydrophilic / repellent patterning film. is there. Unlike the conventional parylene film, the new repellent patterning film of the present invention is also preferable in that it can prevent the occurrence of defects when the aqueous metal nano ink is applied.

In the present invention, the hydrophilic / repellent patterning is preferably performed by irradiating vacuum / ultraviolet pattern (VUV) having a wavelength of 10 nm to 200 nm to the hydrophilic / repellent patterning film through a photomask having a chromium pattern. The distance between the light source and the film and the distance between the mask and the film are appropriately selected depending on the composition of the hydrophilic / repellent patterning film to be used. In addition, when irradiating VUV, it can be performed under a gas having various compositions ranging from the atmosphere to nitrogen. The irradiation time of VUV is not limited as long as good repellent patterning can be performed, but it is more suitable for preventing film deterioration and more suitable for receptive patterning. A range is preferable.

A hydrophilic pattern is drawn on the hydrophobic film by the hydrophilic / repellent patterning. In this case, the contact angles of the hydrophobic region and the hydrophilic region with respect to water are preferably 100 ° or more and 20 ° or less, respectively. The difference in contact angle is preferably 80 ° or more. In addition, the surface tension difference between the hydrophobic region and the hydrophilic region is preferably 40 mN / m. In this state, when dried and heated and fired as necessary, a fine metal wiring pattern having a micrometer size can be more suitably formed. The drying temperature and the baking temperature are not limited as long as the substrate and the hydrophilic / repellent patterning film are not affected. The drying temperature is preferably 10 to 50 ° C., and the heating and baking temperature is preferably 100 to 180 ° C. It is done.

The resolution in the hydrophobic / repellent patterning film is appropriately selected depending on the application, but is preferably 10 μm or less from the viewpoint of practicality. Here, in the present invention, “resolution” refers to a pattern in which a linear electrode wiring (line) having a width of A micron is optically patterned using a mask in which A micron intervals (spaces) are arranged at equal intervals, and then metal When wiring is formed with nano ink, it means the minimum value of A that can form wiring with the shape of a mask. In this case, the line and space is A micron resolution.

When the resin of the present invention is used as a hydrophobic / repellent patterning film, the metal nanoink that can be used in the present invention and the concentration of metal nanoparticles contained in the ink are not limited as long as a low-resistance metal wiring can be formed. However, examples include inks containing metal nanoparticles such as gold, silver, platinum, etc., and solids concentrations of, for example, 5 to 50 wt% can be mentioned. Further, an ink using water or a water / alcohol mixed solvent is exemplified as a medium for dispersing the metal nanoparticles. The type of alcohol is not limited as long as it is compatible with water, and examples thereof include methanol and ethanol.

In the case where an electrode is formed by using the planarization film obtained from the resin of the present invention as a hydrophilic / repellent patterning film, the threshold value of the FET element is used from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode The voltage is preferably more than 0 and not more than 2.0V, or more than −8.0V and less than 0V, more preferably more than 0 and less than 2.0V, or more than −2.0V and less than 0V.

In the case where an electrode is formed using the planarizing film obtained from the resin of the present invention as a hydrophilic / repellent patterning film, the FET element is moved from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode. The degree is preferably 0.20 cm ² / Vs or more.

In the case where an electrode is formed by using a planarizing film obtained from the resin of the present invention as a hydrophilic / repellent patterning film, the FET element is turned on from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode. The current / off-current ratio is preferably 10 ⁶ or more.

In the case where an electrode is formed using the planarizing film obtained from the resin of the present invention as a hydrophilic / repellent patterning film, from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode, the source of the FET element -It is preferable that there is no hysteresis of current between drains.

In the OFET, a substrate that can be used is not particularly limited as long as sufficient flatness capable of producing an element can be secured. For example, glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, Inorganic tin oxide and other inorganic material substrates; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated papers; surface-coated non-woven fabrics, and the like. A multilayered material may be used. Moreover, in order to adjust surface tension, the surface of these materials can also be coated.

Plastics used as the substrate include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene / vinyl acetate copolymer, polymethylpentene-1, and polypropylene. , Cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), poly (diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, Polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer Tomah, styrene block copolymer and the like. Moreover, it can laminate | stack using said plastics 2 or more types, and can be used as a base material.

Examples of the conductive gate electrode, source electrode, or drain electrode that can be used in the present invention include gold, silver, aluminum, copper, titanium, platinum, chromium, polysilicon, silicide, indium / tin / oxide (ITO), A conductive material such as tin oxide is exemplified. In addition, a plurality of these conductive materials can be stacked.

The electrode formation method is not particularly limited, and examples thereof include vapor deposition, high-frequency sputtering, electron beam sputtering, and the like. Using an ink in which nanoparticles of the conductive material are dissolved in water or an organic solvent, solution spin coating, drop Methods such as casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, ink jet printing, letterpress reverse printing and the like can also be employed. Moreover, you may perform the process which makes a fluoroalkyl thiol, a fluoro allyl thiol, etc. adsorb | suck on an electrode as needed.

The organic semiconductor that can be used in the present invention is not limited at all, and any of N-type and P-type organic semiconductors can be used, and can be used as a bipolar transistor that combines N-type and P-type. Examples are (F-1) to (F-10).

In the present invention, both low-molecular and high-molecular organic semiconductors can be used, and these can be used in combination.

In the present invention, examples of the method for forming the organic semiconductor layer include a method in which the organic semiconductor is vacuum-deposited, a method in which the organic semiconductor is dissolved in an organic solvent, and a method for coating and printing. There is no limitation as long as it can be formed. The concentration of the solution when the organic semiconductor layer is applied or printed using a solution in which the organic semiconductor layer is dissolved in an organic solvent varies depending on the structure of the organic semiconductor and the solvent to be used. Therefore, the content is preferably 0.5% to 5% by weight. The organic solvent at this time is not limited as long as the organic semiconductor dissolves at a certain concentration capable of forming a film, and is hexane, heptane, octane, decane, dodecane, tetradecane, decalin, indane, 1-methylnaphthalene, 2-ethyl. Naphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1 , 2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, Tylene 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, 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, di Propylene glycol dimethyl ether 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, cyclohexanone, a Ton, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N, N-dimethylformamide, N-methyl-2-pyrrolidone, limonene and the like are exemplified. Suitable solvents are those having a high boiling point and a boiling point of 100 ° C. or higher, xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, decahydro- 2-Naphthol is preferred. Moreover, the mixed solvent which mixed 2 or more types of the above-mentioned solvent in the appropriate ratio can also be used.

If necessary, various organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added as solids or as dispersions in which nanoparticles are dispersed in water or an organic solvent. A protective film can be formed by applying a polymer solution on the body layer. Furthermore, various moisture-proof coatings and light-resistant coatings can be applied on the protective film as necessary.

According to the present invention, solubility in general-purpose solvents, crosslinking temperature, time required for crosslinking, solvent resistance (crack resistance), dielectric breakdown strength, leakage current, wettability to solvent, and flatness in the case of a film, A resin suitable for a polymer dielectric layer having excellent performance can be provided.

FIG. 2 is a diagram showing a cross-sectional shape of a bottom gate-bottom contact (BGBC) type element. FIG. 2 is a view showing a ¹ H-NMR chart of Resin 1 produced in Example 1. The hysteresis between the source-drain current (I _SD ) (solid line) observed when the gate voltage (V _GS ) is changed in the OFET device manufactured in Example 1 is not observed, and the leakage current value (I _L ) (Broken line) is a figure showing that it is as small as 0.01 nA or less. FIG. 2 is a view showing a cross-sectional shape of a top gate / bottom contact (TGBC) type element; FIG. 10 is a view showing a test pattern of an Ag wiring formed by repellent patterning in Example 9.

Hereinafter, the present invention will be described in more detail 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 production method described in JP-A-2015-224238. Among the photocyclizing compounds used, 2-oxo-2H-1-benzopyran-6-carbonyl chloride (the following formula (G)) is 4- [2- (4-pyridinyl) ethenyl] benzoyl chloride (formula (G)) according to CN 103183634. The following formula (H)) was synthesized in accordance with the method described in Journard-Fur Practice Hemi, Vol. 6, p. 72 (1958). Moreover, the cinnamate chloride (following formula (I)) used the reagent made from Tokyo Chemical Industry. A compound having a fluoroalkyl group (the following formula (J)) was synthesized according to the method described in Journal of Fluorine Chemistry, vol. 131, page 621 (2010). Further, Ag nano ink (ink containing silver nanoparticles) was silver nano colloid H-1 manufactured by Mitsubishi Materials Corporation.

In Examples, NMR, spin coating, film thickness measurement, dispenser printing, UV irradiation, vacuum deposition, UV irradiation amount necessary for crosslinking, wettability of polymer dielectric layer to solvent, dielectric breakdown strength, evaluation of OFET element, The solvent resistance (crack resistance) was evaluated under the following conditions and equipment.
<NMR>
Measurement was performed using JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.). The mole fraction X of the photocyclization group in the aromatic group can be obtained by the following formula using the integrated intensity of the peak obtained by ¹ H-NMR measurement.

X = (P−1) × I ₂ / {(N + 1) × I ₂ −M × I ₁ }
(Where I ₁ represents the integrated value of the peak existing at δ0.8 to δ2.04 ppm, I ₂ represents the integrated value of the peak present at δ6.50 to δ7.6 ppm, and P is present in the photocyclization group. N represents the total number of methylene, methine, and methyl groups, and M represents the total number of hydrogens in the aromatic group.)
<Spin coat>
MS-A100 manufactured by Mikasa Corporation was used.
<Film thickness measurement>
Measurements were made using a Bruker DektakXT stylus profiler.
<Dispenser printing>
An IMAGE MASTER 350PC SMART manufactured by Musashi Engineering Co., Ltd. was used.
<UV irradiation>
Using UV-System and CSN-40A-2 manufactured by GS Yuasa Corporation, the UV irradiation time was adjusted by changing the transport speed under the condition of UV intensity of 4.0 kW.
<Vacuum deposition>
A small vacuum deposition apparatus VTR-350M / ERH manufactured by ULVAC KIKOH Co., Ltd. was used.
<UV irradiation amount necessary for crosslinking>
A resin solution was spin-coated on a washed and dried 30 × 30 mm ² glass (Eagle XG manufactured by Corning) to a film thickness of 500 nm and sufficiently dried. After measuring the initial film thickness (A) at this time, the crosslinked film obtained by changing the UV irradiation amount was immersed in toluene for 1 hour, and the film thickness (B) after drying was measured. Using these film thicknesses, the following formula: remaining film ratio = film thickness (B) / initial film thickness (A) × 100
The UV irradiation amount at which the remaining film ratio given in (1) was 95% or more was determined as the irradiation amount necessary for crosslinking.
<Wettability of polymer dielectric layer to solvent>
1 μL of each of five types of solvents (toluene, tetralin, xylene, mesitylene, chlorobenzene) having different surface tensions was dropped on the crosslinked resin film. When an appropriate amount of the organic semiconductor solution covering the S electrode and the D electrode is applied, it is possible to cover all over the electrode if the shape at the moment when the droplet is applied is maintained or if it spreads wet. It was evaluated as (1 point). On the other hand, when the droplet contracts and / or moves, the electrode cannot be covered, and thus the case where the liquid contracts and / or moves is evaluated as defective (0 point). The score is 5 when good results are obtained with all solvents.
<Dielectric breakdown strength>
Silver was vacuum-deposited on washed and dried 30 × 30 mm ² glass (Eagle XG manufactured by Corning) to form an electrode having a thickness of 30 nm. Thereafter, a dielectric (insulator) is formed on the substrate on which the electrode is formed, and a gold electrode is vacuum-deposited on the dielectric layer to produce an MIM capacitor, and a voltage is applied between the silver-gold electrode. Thus, the voltage at which current starts to flow inside the dielectric layer due to dielectric breakdown was measured, and the value divided by the thickness of the dielectric layer was taken as the dielectric breakdown strength.
<Evaluation of FET element>
A bottom gate / bottom contact (BGBC) type element, which is one form of an organic field effect transistor, is manufactured, and the gate voltage is changed by using a semiconductor parameter analyzer SCS4200 manufactured by Keithley, with a source-drain voltage of minus 60 volts. Thus, mobility, leakage current, on-current / off-current ratio, source-drain current hysteresis, and threshold voltage were evaluated.
<Solvent resistance (crack resistance)>
An insulating film having a thickness of 600 nm was formed on a PET film (made by Teijin DuPont Film) having a size of 5 cm × 5 cm and a thickness of 100 microns using a spin coater, and then photocyclization (photocrosslinking) was performed. This film was immersed in toluene for 1 hour and then taken out, and the toluene was volatilized at room temperature. The film surface was checked for the presence or absence of microcracks on the film surface with a shape measurement laser microscope (VK-X100 manufactured by Keyence Corporation).

Examples are shown below, but the reaction, purification, and drying were all performed under yellow light or under light shielding. In the examples, the reason why the reaction was performed under yellow light or under light shielding was to prevent the photocyclization reaction of the photocyclizable compound and the photocyclization reaction of the resin into which the photocyclizable compound was introduced.
<VUV irradiation>
Irradiation was performed by adjusting the irradiation time using SUS740 manufactured by USHIO INC.
<Blade coat>
Blade coating was performed using an automatic film applicator 100-5 manufactured by Allgood Co., Ltd. and a film applicator 064- 13 with a film thickness adjusting function.
<Formation of polyparaxylylene (parylene) film>
Parylene dimer was introduced into PDS2010 manufactured by Japan Parylene LLC and a film was formed by chemical vapor deposition.
<Evaluation of repellent patterning performance>
Washed and dried 30 × 30 mm ² glass (base material) (Eagle XG manufactured by Corning) was spin-coated with a resin xylene solution (3 wt%) at 500 rpm × 5 seconds and 1500 rpm × 20 seconds at 50 ° C. After drying for 1 minute, a planarized film was formed by irradiation with ultraviolet rays. Thereafter, the surface of the planarizing film was patterned into a lyophilic portion and a lyophobic portion by irradiating with vacuum ultraviolet rays (VUV) through a photomask having a chromium pattern with a line and space of 5 to 50 microns. This substrate is placed in an automatic film applicator body heated to 70 ° C., and after dropping Ag nano ink, the film applicator with film thickness adjusting function is moved at a speed of 140 mm / s, coating is performed, and baking is performed at 120 ° C. for 30 minutes. did. All the formed patterns were observed, and the smallest line and space value among the patterns formed without defects was defined as the resolution.
Example 1
<Resin synthesis>
In a nitrogen box, a 300 mL Schlenk tube was charged with 5.0 g of polystyrene having a weight average molecular weight of 280,000 (hereinafter referred to as “raw polymer A”), 150 mL of dehydrated methylene chloride, and 4.0 g of cinnamic acid chloride. Dissolved. 9.0 g of trifluoromethanesulfonic acid (hereinafter referred to as “TFMS”) was charged into a 30 mL dropping funnel having a three-way cock attached to the upper portion and the lower portion sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, the Schlenk tube was cooled with ice water, and TFMS was dropped from the dropping funnel over 10 minutes. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 28 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 10.6 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to obtain 6.8 g. Of resin 1 was obtained.

As a result of analysis by ¹ H-NMR, it was confirmed that the obtained resin 1 (the following formula) had 59 mol% and 41 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

A ¹ H-NMR chart relating to Resin 1 is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 2.04 ( brs, —CH ₂ —CH—), 1.78 to 1.40 (bm, —CH ₂ —)
<Creation and evaluation of FET element>
Aluminum was vacuum-deposited on washed and dried 30 × 30 mm ² glass (base material) (Eagle XG manufactured by Corning) to form a gate electrode having a thickness of 50 nm. A toluene solution (3 wt%) of the obtained resin 1 was spin-coated on the substrate on which the electrode was formed under the conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds, and dried at 50 ° C. for 5 minutes (insulation) Formation of Film) A polymer dielectric layer having a thickness of 520 nm was formed by irradiation with 250 mJ / cm ² of ultraviolet rays. Gold was vacuum-deposited on the substrate on which the gate electrode and the polymer dielectric layer were formed to form a source electrode and a drain electrode having a thickness of 50 nm, a channel length of 100 μm, and a channel width of 500 μm. Thereafter, it was immediately immersed in an isopropanol solution of pentafluorobenzenethiol 30 mmol / L, taken out after 5 minutes, washed with isopropanol, and blow-dried. Thereafter, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was printed by a dispenser. After the solvent was volatilized and dried at 50 ° C. for 1 hour, a bottom gate / bottom contact (BGBC) type organic field effect transistor device was fabricated. The evaluation results and the like of the produced organic field effect transistor device are shown in Table 1.

As a result of evaluating this element by changing the gate-source voltage by setting the drain-source voltage V _DS to −60 volts, the mobility was 0.36 cm ² / V · s, the leakage current was 0.01 nA, the source-source voltage was There is no hysteresis in the drain-to-drain current, the on-current / off-current ratio is 10 ⁷ or more, and the dielectric breakdown strength is 4 MV / cm or more. Excellent leakage current, hysteresis, on-current / off-current ratio, and dielectric breakdown strength No cracks occurred in the organic semiconductor layer and the insulating film. The fact that the hysteresis is not seen is shown in FIG.
(Example 2)
In a nitrogen box, a 300 mL Schlenk tube was charged with 10 g of the starting polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride, and dissolved under stirring at room temperature. 26 g of TFMS was charged into a 100 mL dropping funnel with a three-way cock attached to the top and the bottom sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, the Schlenk tube was cooled with ice water, and TFMS was dropped from the dropping funnel over 10 minutes. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice water bath was removed and the reaction was allowed to proceed at room temperature for 55 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 36 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities and decolorized, and then reprecipitated with 3 L of methanol. Furthermore, the polymer was purified by reprecipitation and dried under reduced pressure at 50 ° C. to obtain 18.2 g of Resin 2.

As a result of analysis by ¹ H-NMR, the obtained resin 2 (the following formula) has 30 mol% and 70 mol% of the structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 2.04 ( brs, —CH ₂ —CH—), 1.78 to 1.40 (bm, —CH ₂ —)
An organic field effect transistor device was fabricated after an insulating film was formed using the same method as in Example 1 using the resin 2 produced in Example 2. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 3)
Resin 3 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 3 (the following formula) has 75 mol% and 25 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.82 (brs, —CH═CH—C (O) —), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 3 using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
Example 4
Resin 4 was obtained in the same manner as in Example 1, except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride.

As a result of analysis by ¹ H-NMR, it was found that the obtained resin 4 (the following formula) had 60 mol% and 40 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.82 (brs, —CH═CH—C (O) —), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 4 using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 5)
Resin 5 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.

As a result of analysis by ¹ H-NMR, it was found that the obtained resin 5 (the following formula) had 72 mol% and 28 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 ( brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 5 in the same manner as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 6)
Resin 6 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 6 (the following formula) has 58 mol% and 42 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 ( brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
Using the obtained resin 6, an insulating film was formed using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 7)
Resin 7 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 7 (the following formula) has 60 mol% and 40 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 7 in the same manner as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 8)
Resin 8 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 8 (the following formula) has 40 mol% and 60 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 8 using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
Example 9
Polystyrene-b-poly (ethylene propylene) -b-polystyrene (SEPS) having a weight average molecular weight of 150,000 and a polystyrene content of 65 wt% in a 300 mL Schlenk tube in a nitrogen box (hereinafter referred to as “raw polymer B”) 4 .01 g, 150 mL of dehydrated methylene chloride, and 4.5 g of cinnamic acid chloride were charged and dissolved under stirring at room temperature. Next, the Schlenk tube was cooled to 0 ° C. or lower, and 6.2 g of TFMS was dropped using a syringe. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 24 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 6.9 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities and decolorized, and then reprecipitated with 1.5 L of methanol. Further, the polymer was purified by reprecipitation twice and dried under reduced pressure at 40 ° C. to obtain 5.6 g of resin 9.

As a result of analysis by ¹ H-NMR, the obtained resin 9 (the following formula) has 27 mol% and 29 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.59 (brs, —CH═CH—Ph), 7.36 (brs, aromatic), 6.99 (brs, aromatic), 6.45 (brs) , —CH═CH—Ph), 1.90 to 1.00 (bm, —CH ₂ —), 0.84 (bm, —CH ₃ )
<Evaluation of repellent patterning performance>
It was confirmed that all of the 5 to 50 micron line and space patterns were satisfactorily drawn, and that there was a resolution of 5 microns. Further, the surface roughness of the obtained film was 0.3 nm and the flatness was excellent.
<Creation and evaluation of organic TFT element>
The xylene solution (3 wt%) of the resin 9 obtained was spin-coated on the cleaned and dried 30 × 30 mm ² glass (base material) (Eagle XG manufactured by Corning) under the conditions of 500 rpm × 5 seconds and 1500 rpm × 20 seconds. After drying at 50 ° C. for 5 minutes, an undercoat film having a thickness of 100 nm was formed by irradiation with ultraviolet rays of 100 mJ / cm ² . Then, VUV was irradiated for 180 seconds through the photomask, and the surface of the base film was patterned to be lyophilic and liquid repellent. This substrate is placed on an automatic film applicator body heated to 70 ° C., and after Ag nanoink is dropped, the film applicator with a film thickness adjusting function is applied at a speed of 140 mm / s, coating is performed, and baking is performed at 120 ° C. for 30 minutes. Thus, a source electrode and a drain electrode having a thickness of 500 nm, a channel length of 5 μm, a channel width of 500 μm, and an electrode width of 100 μm were formed. Thereafter, it was immediately immersed in an isopropanol solution of pentafluorobenzenethiol 30 mmol / L, taken out after 5 minutes, washed with isopropanol, and blow-dried. Thereafter, a 0.8 wt% xylene / tetralin mixed solution of an organic semiconductor (di-n-hexyldithienobenzothiophene) was formed by spin coating. In order to volatilize the solvent, it was dried at 90 ° C. for 20 minutes. Thereafter, 0.6 g of the obtained substrate and parylene dimer are placed in a vacuum vapor deposition device, heated in vacuum to vaporize the parylene dimer, polymerized on the substrate, and gate insulation composed of polyparaxylylene having a thickness of 430 nm. Layers were deposited. Thereafter, VUV was irradiated for 180 seconds through a photomask, and the surface of the gate insulating film was patterned to be lyophilic and lyophobic. This substrate is placed in an automatic film applicator body heated to 70 ° C, and after dropping Ag nano ink, it is applied at a rate of 140 mm / s and baked at 90 ° C for 20 minutes to form a gate electrode having a thickness of 500 nm. A top gate / bottom contact (TGBC) type organic field effect transistor device was fabricated. The structure of the produced organic field effect transistor is shown in FIG.

As a result of evaluating this element by changing the gate-source voltage with the drain-source voltage V _{DS set} to -60 volts, the mobility was 0.3 cm ² / V · s, the leakage current was 0.01 nA, the source-source voltage was There is no hysteresis in the drain-to-drain current, the on-current / off-current ratio is 10 ⁷ or more, and the dielectric breakdown strength is 4 MV / cm or more. Excellent leakage current, hysteresis, on-current / off-current ratio, and dielectric breakdown strength No cracks occurred in the organic semiconductor layer and the base film.
(Example 10)
In a nitrogen box, a 300 mL Schlenk tube was charged with 4.01 g of the raw material polymer B, 150 mL of dehydrated methylene chloride, and 5.99 g of cinnamic acid chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled to 0 ° C. or lower, and 8.2 g of TFMS was dropped using a syringe. The color of the polymer solution colored reddish purple as it was dropped. After completion of dropping, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 25 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 9.14 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities and decolorized, and then reprecipitated with 1.5 L of methanol. Further, the polymer was purified by reprecipitation and dried under reduced pressure at 40 ° C. to obtain 6.0 g of resin 10.

As a result of analysis by ¹ H-NMR, the obtained resin 10 (the following formula) has 21 mol% and 32 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.59 (brs, —CH═CH—Ph), 7.36 (brs, aromatic), 6.99 (brs, aromatic), 6.45 (brs) , —CH═CH—Ph), 1.90 to 1.00 (bm, —CH ₂ —), 0.84 (bm, —CH ₃ )
<Evaluation of repellent patterning performance>
Evaluation was made in the same manner as in Example 9, and it was confirmed that good drawing was achieved with all the lines and spaces of 5 to 50 microns, and that there was a resolution of 5 microns. The obtained film had a surface roughness of 0.3 nm and excellent flatness.
<Creation and evaluation of organic TFT element>
A top gate / bottom contact (TGBC) type organic field effect transistor device was fabricated in the same manner as in Example 9. The evaluation results of the produced organic field effect transistor are shown in Table 1.

As in Example 9, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 11)
In a nitrogen box, a 300 mL Schlenk tube was charged with 3.0 g of raw material polymer B, 150 mL of dehydrated methylene chloride, and 6.3 g of cinnamic acid chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled to 0 ° C. or lower, and 8.44 g of TFMS was added dropwise using a syringe. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 29 hours. After the reaction solution was cooled again with ice water, a saturated aqueous solution in which 9.45 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities and decolorized, and then reprecipitated with 1.5 L of methanol. Furthermore, the polymer was purified by reprecipitation and dried under reduced pressure at 40 ° C. to obtain 4.9 g of resin 11.

As a result of analysis by ¹ H-NMR, the obtained resin 11 (the following formula) has 17 mol% and 39 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

As in Example 9, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 12)
In a nitrogen box, a 300 mL Schlenk tube was charged with 10 g of the starting polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride, and dissolved under stirring at room temperature. 26 g of TFMS was charged into a 100 mL dropping funnel with a three-way cock attached to the top and the bottom sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, it cooled in the low temperature thermostat, and TFMS was dripped over 10 minutes from the dropping funnel, stirring with a magnetic stirrer. The color of the polymer solution colored reddish purple as it was dropped. After completion of dropping, the reaction was carried out at 1 ° C. for 55 hours. Of 360 mL of saturated aqueous solution in which 36 g of saturated sodium bicarbonate was dissolved, 100 mL was slowly added dropwise. The remaining saturated sodium bicarbonate solution was placed in a 1 L beaker, and 100 g of ice was added and cooled. The reaction solution was poured into this beaker and stirred for 2 hours, and then transferred to a separatory funnel to separate the methylene chloride layer. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. The polymer solution was reprecipitated with 3 L of methanol twice, filtered and dried under reduced pressure at 50 ° C. to obtain 17.9 g of resin 12.

As a result of analysis by ¹ H-NMR, the obtained resin 12 (the following formula) was obtained by converting the structural units represented by the formula (1), the formula (2) and the formula (18) to 36.5 mol% and 62.5 It was confirmed that they had mol% and 1.0 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), δ4.5 ( brs, —C (O) CH ₂ —CH (Ph) —), δ2.57 (brs, —C (O) CH ₂ —CH (Ph) —), δ3.14 (brs, —C (O) CH ₂ —CH (Ph) —), 2.04 (brs, —CH ₂ —CH—), 1.78 to 1.40 (bm, —CH ₂ —)
An insulating film was formed using the obtained resin 12 using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
(Example 13)
In a nitrogen box, a 300 mL Schlenk tube was charged with 1.1 g of the raw material polymer B, 30 mL of dehydrated methylene chloride and 1.3 g of 3- (perfluorohexyl) propionyl chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled with ice water, and 1.2 g of TFMS was added dropwise using a syringe under a nitrogen flow. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed for 48 hours at room temperature. The reaction solution was cooled again with ice water, and then an aqueous solution in which 1.2 g of sodium bicarbonate was dissolved was added dropwise to neutralize TFMS and hydrochloric acid in the system. The reaction solution was transferred to a separatory funnel and the aqueous phase was separated. Further, the methylene chloride phase was washed with water three times and separated to obtain a methylene chloride solution of the polymer. This solution was reprecipitated with 300 mL of methanol. Further, the polymer was purified by reprecipitation twice and dried under reduced pressure at 40 ° C. to obtain 1.7 g of resin 13-a (the following formula).

Further, 1.0 g of the resin 13-a obtained in a 100 mL Schlenk tube, 40 mL of dehydrated methylene chloride, and 0.59 g of cinnamic acid chloride were charged in a nitrogen box and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled with ice water, and 1.3 g of TFMS was added dropwise using a syringe under a nitrogen flow. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice water bath was removed and the reaction was allowed to proceed for 48 hours at room temperature. The reaction solution was cooled again with ice water, and then an aqueous solution in which 1.2 g of sodium bicarbonate was dissolved was added dropwise to neutralize TFMS and hydrochloric acid in the system. The reaction solution was transferred to a separatory funnel and the aqueous phase was separated. Further, the methylene chloride phase was washed with water three times and separated to obtain a methylene chloride solution of the polymer. This solution was reprecipitated with 350 mL of methanol. Furthermore, the polymer was purified by reprecipitation twice and dried under reduced pressure at 40 ° C. to obtain 1.1 g of resin 13.

As a result of analysis by ¹ H-NMR, the obtained resin 13 (the following formula) was obtained by adding 3 mol%, 29 mol%, and 29 mol% of structural units represented by formula (1), formula (2), and formula (19), respectively. And 24 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.62 (brs, aromatic, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 3 .12 (brs, —CH ₂ —C (═O) —), 2.52 (brs, —CF ₂ —CH ₂ —), 1.90 to 1.00 (bm, —CH ₂ —), 0. 84 (bm, —CH ₃ )
An insulating film was formed using the obtained resin 13 using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
<Evaluation of repellent patterning performance>
Evaluation was made in the same manner as in Example 9, and it was confirmed that good drawing was achieved with all the lines and spaces of 5 to 50 microns, and that there was a resolution of 5 microns. The obtained film had a surface roughness of 0.3 nm and excellent flatness.
(Comparative Example 1)
In a nitrogen box, a 300 mL Schlenk tube was charged with 5.0 g of the starting polymer A, 150 mL of dehydrated methylene chloride, and 3.9 g of anhydrous aluminum chloride, and dissolved at room temperature with stirring. A 30-mL dropping funnel with a three-way cock attached to the upper part and a sealed lower part was charged with 30 mL of methylene chloride solution of 4.0 g of cinnamic acid chloride. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, the Schlenk tube was cooled with ice water, and cinnamic acid chloride was dropped from the dropping funnel over 10 minutes. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 28 hours. The reaction solution was cooled again with ice water, and 20 mL of 35% aqueous hydrochloric acid was added dropwise. After stirring in this state for 5 hours, the reaction solution was transferred to a separatory funnel, and the methylene chloride layer was separated. This methylene chloride layer was washed with water repeatedly 4 times. The aqueous layer was extracted three times with methylene chloride and separated. The obtained methylene chloride layers were combined, filtered through a 3 μm Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice. Drying gave 5.9 g of resin 14.

As a result of analysis by ¹ H-NMR, the obtained resin 14 (the following formula) has 86 mol% and 14 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 2.04 ( brs, —CH ₂ —CH—), 1.78 to 1.40 (bm, —CH ₂ —)
Using the obtained resin, an insulating film was formed using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 2)
In a nitrogen box, a 300 mL Schlenk tube was charged with 5.0 g of raw material polymer A, 150 mL of dehydrated methylene chloride, and 1.2 g of anhydrous aluminum chloride. A three-way cock was attached to the upper part, and a solution of 1.3 g of cinnamic acid chloride dissolved in 20 mL of methylene chloride was charged into a 30 mL dropping funnel with the lower part sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, the Schlenk tube was cooled with ice water, and cinnamic acid chloride was dropped from the dropping funnel over 10 minutes. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 28 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 2.1 g of saturated sodium bicarbonate was dissolved was added to neutralize hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to 4.7 g Of resin 15 was obtained.

As a result of analysis by ¹ H-NMR, the obtained resin 15 (the following formula) has 92 mol% and 8 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 3)
In a nitrogen box, a 300 mL Schlenk tube was charged with 5 g of the raw material polymer A, 150 mL of dehydrated methylene chloride, and 2.2 g of anhydrous aluminum chloride. A solution in which 2.3 g of cinnamic acid chloride was dissolved in 50 mL of methylene chloride was charged into a 20 mL dropping funnel with a three-way cock attached to the top and the bottom sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. The nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped. Next, the Schlenk tube was cooled with ice water, and cinnamic acid chloride was dropped from the dropping funnel over 9 minutes. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 28 hours. The reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 3.9 g of saturated sodium bicarbonate was dissolved was added to neutralize hydrochloric acid in the system. The reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 μm Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to obtain 4.9 g. Of resin 16 was obtained.

As a result of analysis by ¹ H-NMR, the obtained resin 16 (the following formula) has 87 mol% and 13 mol% of the structural units represented by formula (1) and formula (2), respectively. confirmed.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 4)
Resin 17 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride. The analysis results by ¹ H-NMR (400 MHz, CDCl ₃ ) and the structural formula of the polymer are shown below.

As a result of analysis by ¹ H-NMR, it was found that the obtained resin 17 (the following formula) had 94 mol% and 6 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.82 (brs, —CH═CH—C (O) —), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
Using the obtained resin, an insulating film was formed using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 5)
Resin 18 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride.

As a result of analysis by ¹ H-NMR, it was confirmed that the obtained resin 18 (the following formula) had 88 mol% and 12 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 6)
Resin 19 was obtained in the same manner as in Comparative Example 1, except that cinnamic acid chloride was changed to pyridinylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, it was found that the obtained resin 19 (the following formula) had 94 mol% and 6 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 ( brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
Using the obtained resin, an insulating film was formed using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 7)
Resin 20 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to pyridinylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 20 (the following formula) has 86 mol% and 14 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 8)
Resin 21 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, it was found that the obtained resin 21 (the following formula) had 95 mol% and 5 mol% of the structural units represented by formula (1) and formula (2), respectively. confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—), 2.15 (brs, —CH ₂ —CH—), 1.90 to 1.48 (bm, —CH ₂ —)
Using the obtained resin, an insulating film was formed using the same method as in Example 1, and then an organic field effect transistor device was produced. The evaluation results and the like of the produced organic field effect transistor device are shown together in Table 1.

Compared with Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.
(Comparative Example 9)
Resin 22 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.

As a result of analysis by ¹ H-NMR, the obtained resin 22 (the following formula) has 85 mol% and 15 mol% of the structural units represented by the formulas (1) and (2), respectively. It was confirmed.

Compared to Examples 1 to 8, it was confirmed that the crosslinking time, solvent resistance (crack resistance), and dielectric breakdown strength were inferior.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Japanese Patent Application No. 2017-051670 filed on March 16, 2017, Japanese Patent Application No. 2017-194489 filed on October 13, 2017, Japanese Patent Application filed on January 26, 2018 The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2018-011580 and Japanese Patent Application No. 2018-011580 filed on Jan. 26, 2018 are incorporated herein by reference. It is incorporated as a disclosure.

Claims

A resin comprising repeating units represented by formula (1) and formula (2), wherein the repeating unit of formula (2) is 20 mol% based on the total number of repeating units of formula (1) and formula (2). Resin containing above.

(In the formula (1), R 1 represents hydrogen or a C1-C6 alkyl group, S 1 represents —O— or —C (O) —, p represents 0 or 1, and A 1 represents a C6-C19 aryl. Y represents a halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group, and k represents 0 to (s-1 Where s represents the number of carbon atoms constituting A 1. )

{(In the formula (2), R 2 represents hydrogen or a C1-C6 alkyl group, S 2 represents —O— or —C (O) —, q represents 0 or 1, and A 2 represents C6 to C19. Y represents an 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), where r Represents the number of carbon atoms constituting A 2. Z represents at least one organic group selected from formulas (A) to (D).

(In the formulas (A) to (D), R 3 and R 4 each independently represent hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group, and R 5 to R 29 each independently represent Represents hydrogen, halogen, cyano group, carboxyalkyl group, alkyl ether group, aryl ether group, C1-C18 alkyl group, fluoroalkyl group, or cycloalkyl group)}
An insulating film comprising the cross-linked product of the resin according to claim 1.
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 stacked on a substrate via a gate insulating layer, and the gate insulating layer is the insulating film according to claim 2. An organic field effect transistor device.
A planarization film comprising the resin according to claim 1 and / or a crosslinked product of the resin according to claim 1.
A hydrophilic / repellent patterning film comprising the resin according to claim 1 and / or a crosslinked product of the resin according to claim 1.