WO2019181954A1

WO2019181954A1 - Polymerizable compound, photocurable polymer, insulating film, protective film, and organic transistor device

Info

Publication number: WO2019181954A1
Application number: PCT/JP2019/011494
Authority: WO
Inventors: 山川浩
Original assignee: 東ソー株式会社
Priority date: 2018-03-23
Filing date: 2019-03-19
Publication date: 2019-09-26

Abstract

Provided are: a polymer for forming an insulating layer in which contact holes can be formed, the polymer dissolving in a lower aliphatic alcohol and photocrosslinking in a short period of time with ultraviolet rays; a polymer that can be used as an insulating layer in an organic transistor device, dissolves in general-purpose solvents, crosslinks at normal temperature and in a short period of time, and exhibits excellent insulating properties; and a polymer which is soluble in a solvent, can be made insoluble in a solvent by photocrosslinking at ordinary temperature in a short period of time, and is liquid repellent.　A polymerizable compound represented by formula (1) and formula (2). (In formula (1): R₁ is hydrogen or a C1-C6 alkyl group; L is a C1-C14 divalent linking group; n is 0 or 1; A, R₂ and R₃ are each independently one from the group consisting of hydrogen, halogens, cyano groups, nitro groups, C1-C18 alkyl groups, alkoxy groups, alkyl thio groups, alkyl amino groups, alkyl ketone groups, alkyl ester groups, alkyl amido groups, aryl groups, aryl ether groups, aryl thio groups, carboxyalkyl groups, fluoroalkyl groups, fluoroalkoxy groups, fluoroalkyl carbonyl groups, fluoroalkyl ester groups, fluoroaryl groups, fluorothio groups, cycloalkyl groups, and cycloheteroalkyl groups; X is O or S; and m is an integer of 0-3.)　(In formula (2): Q₁ and Q₂ are each independently a C1-C14 divalent linking group; p and q are each independently 0 or 1; G₁, G₂, and R₄-R₇ are each independently a hydrogen, a halogen, a cyano group, a nitro group, a C1-C18 alkyl group, an alkoxy group, an alkyl thio group, an alkyl amino group, an alkyl ketone group, an alkyl ester group, an alkyl amido group, an aryl group, an aryl ether group, an aryl thio group, a carboxyalkyl group, a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkyl carbonyl group, a fluoroalkyl ester group, a fluoroaryl group, a fluorothio group, a cycloalkyl group or a cycloheteroalkyl group; X₁-X₄ are each independently O or S; and r and s are each independently an integer of 0-3.)

Description

Polymerizable compound, photocurable polymer, insulating film, protective film, and organic transistor device

The present invention relates to a polymer for forming an insulating film and a protective film that can be solution-coated on an organic semiconductor layer included in an organic transistor device.

The present invention also relates to a polymer for forming an insulating layer included in an organic transistor device.

The present invention also relates to a polymer suitable for use in an electronic device.

A top gate type organic transistor device manufactured by a full printing method has a flattening layer or an insulating layer (A layer), a lower metal electrode (source, and the like) on a substrate such as a plastic film from the lower surface to the upper surface of the device. A drain electrode), an organic semiconductor layer (B layer), an insulating layer (C layer), and an upper metal electrode (gate electrode) are formed in this order. The organic semiconductor layer is locally formed in a shape covering the source electrode and the drain electrode, and the drain electrode has a shape drawn to the outside of the region where the organic semiconductor layer is formed, and is in contact with the C layer. In addition to the function as the insulating layer, the C layer also serves as a protective film that reduces the influence of the organic semiconductor and the organic transistor device coming into contact with the outside air and deteriorating. The A layer and the C layer are formed by printing a solution obtained by dissolving an insulating polymer in an organic solvent. In forming the C layer, the polymer solution forming the C layer must not dissolve the already formed organic semiconductor layer (B layer). Further, it is necessary to form a contact hole in the C layer. The contact hole is a hole for connecting the drain electrode under the C layer and the driving circuit of the transistor.

Although organic semiconductors have a difference in solubility, they are often dissolved at least partially by various general-purpose organic solvents. Therefore, at present, as a method of forming the C layer on the upper surface of the B layer, for example, a method of forming a polyparaxylylene (PPX) film by vapor deposition is known. Since this method does not use a solvent, the raw material is heated and vapor-deposited onto a substrate under vacuum to form a polyparaxylylene thin film, so that the organic semiconductor layer should not be dissolved by contact with the solvent. I can do it. On the other hand, the PPX film does not dissolve in a general-purpose hydrocarbon solvent at room temperature, and has a fatal defect that it is difficult to form a contact hole. In addition, the method of vapor deposition limits the size of the substrate that can be treated, and it is difficult to continuously manufacture by the entire printing process, and the batch process is inferior in economic efficiency.

As another method, a method in which a solution obtained by dissolving a fluorinated cyclic ether polymer in a fluorinated solvent is coated on the upper surface of the organic semiconductor layer is known. Since many of the currently known organic semiconductors do not dissolve in fluorine-based solvents, an insulating layer of a fluorine-based cyclic ether polymer can be formed on the organic semiconductor layer without affecting the organic semiconductor layer. However, since the fluorine-based cyclic ether polymer and the fluorine-based solvent are inferior in economic efficiency and the solution has low affinity with an organic semiconductor, the fluorine-based cyclic ether polymer layer and the organic semiconductor layer There is also a problem that the performance as an organic field effect transistor device is lowered due to the low adhesion of the film.

¡Even if it is applied to the upper surface of the organic semiconductor layer, it does not affect a wide variety of organic semiconductor layers, and aliphatic alcohol is one of highly versatile solvents. If the high-boiling point aliphatic alcohol remains in the insulating layer, the semiconductor performance is deteriorated, and therefore, a low-boiling point lower aliphatic alcohol is suitable as the solvent. Known resins that dissolve in lower aliphatic alcohols include butyral resin, polyvinyl alcohol, and alkyl methacrylate having a specific structure. However, butyral resin and polyvinyl alcohol have a hydroxyl group, and this hydroxyl group traps electric charge and deteriorates semiconductor performance. Therefore, it is not suitable as a resin for forming an insulating layer. On the other hand, among the alkyl methacrylates, poly (n-butyl methacrylate) and poly (n-octyl methacrylate) are dissolved in lower aliphatic alcohols (Non-patent Document 1), and have no hydroxyl groups, so that they are used as insulating layer materials. When this occurs, the problem of charge trapping is less likely to occur. However, these polymers do not have photocrosslinkability and, when used as an insulating layer, do not exhibit solvent resistance to organic solvents, making it difficult to form contact holes.

From such a background, a polymer that can be dissolved in a lower aliphatic alcohol and that can be crosslinked (cured) is required as a polymer for forming the C layer. As the polymer crosslinking method, a method using heat or radiation is generally used. However, in the cross-linking of the insulating layer formed on the organic semiconductor layer, the cross-linking by heating is not preferable from the viewpoint of suppressing performance degradation due to thermal expansion / contraction of the organic semiconductor layer as much as possible. For this reason, crosslinking by radiation is preferable, and crosslinking by ultraviolet rays (photocrosslinking) is particularly suitable. In photocrosslinking of the C layer by ultraviolet rays, it is preferable to reduce the amount of ultraviolet rays as much as possible in order to prevent deterioration of the organic semiconductor due to radiation that has passed through the optically transparent C layer. From this viewpoint, a polymer for forming a C layer that can be photocrosslinked in a short time is required.

The photocrosslinkable polymer can be obtained by introducing a photocrosslinkable functional group into the main chain or side chain of the polymer. Various photo-crosslinkable functional groups are known, and polycyclic aromatic compounds such as anthracene and tetracene, coumarin (for example, Non-Patent Document 2) are known as those having high chemical stability to radicals. ) And quinolinone are known (for example, Non-Patent Documents 3 and 4). A photocrosslinkable polymer can be obtained by radical copolymerizing a monomer having these functional groups with another monomer.

As a photocrosslinkable polymer in which anthracene is introduced as a photocrosslinking group, for example, as a polymer in which an anthryl group is introduced as a photocrosslinking group, a copolymer of 6- (anthracen-9-yl) hexyl methacrylate and fluoroalkyl methacrylate (Non-patent document 5), diblock copolymer comprising poly (2-ethylhexyl methacrylate) and poly (9-anthrylmethyl methacrylate) (non-patent document 6), 6- (9-anthryloxy) hexyl methacrylate homopolymer A technique related to (Non-Patent Document 7) is disclosed. However, since an anthracene group having a large molecular weight reduces the solubility in a lower alcohol, its introduction amount is limited, and the same applies to tetracene. Therefore, in these polymers, there is an upper limit for the photocrosslinking rate, which cannot cope with the reduction of the irradiation amount of ultraviolet rays, and the short required for continuous production of organic transistors only by printing by the roll-to-roll method. Could not cope with photocrosslinking in time.

As a polymer containing coumarin and quinolinone, for example, a polymer for a liquid crystal alignment film has been proposed (for example, Patent Document 1). However, this polymer has a problem that it does not dissolve in lower aliphatic alcohols.

As described above, there has been a demand for a polymer for forming an insulating layer that can be dissolved in a lower aliphatic alcohol and photocrosslinked with ultraviolet rays in a short time to form a contact hole.

As another problem, an organic transistor device basically includes three electrodes (a source electrode, a drain electrode, and a gate electrode), an insulating layer, and an organic semiconductor layer. Currently, development of technology (all printing methods) for producing organic transistors by printing on plastics such as polyethylene naphthalate film is underway. When an organic transistor is manufactured by a full printing method, the order in which the electrode, the insulating layer, and the organic semiconductor layer are formed differs depending on the form of the organic transistor. For example, by printing an aqueous or non-aqueous ink containing metal nanoparticles. An electrode can be formed by printing a crosslinkable polymer solution, and an organic semiconductor layer can be formed by printing an organic semiconductor solution. An organic solvent is used for the preparation of the polymer solution and the organic semiconductor solution.

So far, it has been proposed to use polyparaxylylene (PPX), benzocyclobutene (BCB) polymer, polyvinylphenol (PVP) composition, and fluorine-based cyclic ether (FCE) polymer as the insulating layer. PPX is excellent in insulation, but does not dissolve in a general-purpose solvent and cannot be applied to the above printing process. The BCB polymer and the PVP composition have high crosslinking temperatures of 150 ° C. and 250 ° C., respectively, and the crosslinking time is also long. For this reason, it is difficult to apply to a continuous production process using a roll-to-roll system. In particular, in the production of an organic transistor device using a plastic as a base material, the plastic of the base material is deformed by heating at the time of crosslinking, so that it is difficult to use other than engineering plastic films such as polyimide having excellent heat resistance. On the other hand, the FCE polymer dissolves in a specific fluorine-based solvent such as perfluorotributylamine (PFTBA) but does not dissolve in a general-purpose organic solvent. The FCE polymer has a small surface tension, and when the organic semiconductor layer solution is printed on the polymer film, the solution does not spread and uniform printing is difficult. Further, the polymer and the solvent were both expensive and inferior in economic efficiency.

From the above background, photocrosslinkable polymers that can be crosslinked at room temperature in a short time are attracting attention. For example, a polymer having a photocrosslinkable cinnamoyl group introduced into a polymer having a hydroxyl group such as poly (hydroxyethyl methacrylate) (for example, see Patent Document 2) and a polymer having a phenol group in the side chain have photocrosslinkability. A polymer into which coumarin is introduced (for example, see Patent Document 3) has been proposed. However, an unreacted hydroxyl group remains in these polymers, and this hydroxyl group has a problem that the dielectric breakdown strength is lowered and the performance as an insulating layer is inferior. Patent Document 2 discloses a technique for reducing the amount of residual hydroxyl group by reacting an unreacted hydroxyl group with trifluoroacetic anhydride. However, it has been extremely difficult to completely eliminate the hydroxyl group by this method.

Also, a vinyl monomer having a photocrosslinkable cinnamoyl group and a copolymer with a fluorine-containing vinyl monomer have been proposed (for example, see Patent Document 4). According to this technique, when the above-mentioned monomer having a cinnamoyl group in the side chain is radically polymerized, the double bond of the cinnamoyl group reacts with the radical to crosslink the polymer to form a gel, resulting in poor film forming properties. There was a problem.

In addition, a technique related to a photocrosslinkable polymer in which a cinnamoyl group having photocrosslinkability is introduced into an aromatic vinyl polymer such as polystyrene by Friedel-Crafts acylation reaction is also disclosed (for example, Patent Document 5, Patent Reference 6). However, this technique has a fatal problem that a gel is generated during the reaction regardless of the amount of cinnamoyl groups introduced, and the reaction solution itself gels when the amount of cinnamoyl groups exceeds a certain amount.

Here, generally, when there is a foreign substance in the insulating layer, the dielectric breakdown strength is lowered, and the flatness of the layer is also lowered, so that problems such as inferior performance of the organic transistor occur. Therefore, the polymer solution must be microfiltered prior to the formation of the insulating layer. However, since the polymers proposed in Patent Documents 4 to 6 contain gel, it is difficult to perform microfiltration economically and with high productivity.

From such a background, there has been a demand for a polymer that dissolves in a general-purpose solvent, does not contain gel, has excellent insulating properties that crosslinks at low temperature in a short time, and an insulating film containing the polymer.

Also, as another issue, in recent years, technological development relating to the manufacture of electronic devices by full printing with low cost and high productivity has been actively carried out. For example, organic transistors are being developed as electronic devices. This organic transistor is manufactured through a number of processes, and includes a process of forming an organic semiconductor film in a specific minute region. This minute region is, for example, a rectangular region on the order of microns including a source electrode and a drain electrode. When an organic semiconductor solution is printed in the region using ink jet, it is necessary to drop the organic semiconductor solution in a minute region and prevent the organic semiconductor solution from getting wet out of the region. As a method for preventing wetting and spreading, a method for preventing the solution from spreading out of the micro area by making only the above micro area lyophilic and making the outside of the area lyophobic is known. Yes. At this time, when a film is provided to prevent wetting and spreading outside the region, the film is called a partition wall. There is also a method of forming a liquid-repellent wall having a certain width and thickness around the minute region, and this wall is also called a partition.

As the material used for forming the partition walls, a fluorine-based resin having a low surface tension that exhibits liquid repellency to water and organic solvents is suitable. Moreover, in order to form this partition wall by printing, a fluorine-based resin that is soluble in a solvent is required. Examples of the fluorine-based resin include perfluorobutenyl ether polymers (product name: Cytop, manufactured by Asahi Glass). Tetrafluoroethylene / perfluorodioxole copolymer (manufactured by Mitsui DuPont Fluorochemicals, trade name Teflon (registered trademark) AF) and the like are known. At this time, a fluorine-based solvent such as fluoroalkylamine is used as the solvent.

When a partition wall is to be formed from the above fluororesin, since the partition wall has a low surface tension, when an insulating film is laminated on the partition wall using another resin, the adhesion between the two resins is low and the electronic device There was a problem that could not be formed.

Although the adhesion problem can be solved by forming the insulating film and the partition with the same material, there is a problem that the partition dissolves when the insulating film is laminated. Here, dissolution of the partition wall greatly reduces the transistor performance due to peeling of the organic semiconductor film due to the flow of the partition wall or loss of uniformity of the insulating film thickness. For this reason, the material for forming the partition walls is required to be capable of being easily printed by being dissolved in a fluorinated solvent, and to be insoluble in the fluorinated solvent when forming the partition walls. A resin crosslinking technique is known as such an insolubilization technique, and photocrosslinking is known as a technique capable of crosslinking in a short time.

As a photocrosslinkable resin, a technique of a polyfluoroalkyl methacrylate copolymer having an azide group introduced has been proposed (see, for example, Patent Document 7). However, when the partition walls are formed from this resin, the photocrosslinking rate is low, so that an ultraviolet irradiation amount of 1 J / cm ² or more is necessary, and the productivity is low. Further, the surface tension was as high as 18 to 23 mN / m, and the liquid repellency was insufficient.

From the above background, a liquid repellent polymer that is soluble in a solvent and insolubilized in a solvent by photocrosslinking at room temperature in a short time has been demanded.

US Pat. No. 6,2010,871 Japanese Patent No. 5148624 Japanese Patent No. 5960202 Japanese Patent No. 5938192 US Pat. No. 2,662,302 U.S. Pat. No. 2,708,665 U.S. Pat. No. 4,365,049

The present invention has been made in view of the above problems, and an object thereof is to provide a polymer for forming an insulating layer which can be dissolved in a lower aliphatic alcohol and photocrosslinked in a short time with ultraviolet rays to form a contact hole. There is to do.

Another object of the present invention is to provide a polymer excellent in insulation that dissolves in a general-purpose solvent that can be used as an insulating layer of an organic transistor device and crosslinks at room temperature in a short time.

Another object is to provide a polymer that is soluble in a solvent, insolubilized in a solvent by photocrosslinking at room temperature in a short time, and exhibits liquid repellency.

As a result of intensive studies to solve the above problems, the present inventors have found that a polymerizable compound having a specific structure and a specific polymer obtained therefrom can solve the above problems, and complete the present invention. It came.

That is, the present invention resides in the following [1] to [10].
[1] A polymerizable compound represented by the following formula (1).

(In the formula (1), R ₁ represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R ₂ and R ₃ is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl One kind of the group consisting of an ether group, an arylthio group, a carboxyalkyl group, a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group X represents O or S, and m represents an integer of 0 to 3.)
[2] A polymerizable compound represented by the following formula (2).

(In Formula (2), Q ₁ and Q ₂ are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1, G ₁ , G ₂ , R ₄ to R ₇ are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group, X ₁ ~ X ₄ each independently are O or S, r and s are each independently an integer of 0 to 3 Represent.)
[3] At least one repeating unit of the group consisting of the following formulas (6) to (8), which is included as at least one repeating unit of the group consisting of the following formulas (3) to (5) A polymer comprising

(In the formula (3), R ₁ represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R ₂ and R ₃ is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl Consists of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group (One of the groups, X represents O or S, and m represents an integer of 0 to 3.)

(In the formula (4), R ₁ represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R ₂ and R ₃ is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl Consists of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group (One of the groups, X represents O or S, and m represents an integer of 0 to 3.)

(In the formula (5), Q ₁ and Q ₂ are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1, G ₁ , G ₂ , R ₄ to R ₇ are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group the one of the group consisting _of, X 1 ~ _{X 4} are each independently O or S, And s each independently represents an integer of 0-3.)

(In the formula (6), R ₈ represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.)

(In the formula (7), R ₉ is either hydrogen or a C1-C6 alkyl group, M is a divalent linking group having 1 to 14 carbon atoms, k is 0 or 1, Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group, and j is 0 to Represents an integer of 5.)

(In formula (8), R ₁₀ represents hydrogen or a C1-C6 alkyl group, E represents —O—, —S—, or —NH—, t represents 0 or 1, and R ₁₁ represents 1 to Represents 18 fluoroalkyl groups.)
[4] The polymer of [3] comprising repeating units represented by the following formula (4) and the following formula (6).

(Here, R ₁ , L, n, A, R ₂ , R ₃ , X and m are the same as those defined in the formula (1).)

(Here, R ₈ represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.)
[5] The polymer according to [3], which contains at least one of the following formula (4) and formula (5) as a repeating unit and further contains a repeating unit represented by the following formula (7).

(Here, Q ₁ , Q ₂ , p, q, G ₁ , G ₂ , R ₄ to R ₇ , X ₁ to X ₄ , r and s are the same as those defined in the formula (2)). .)

(In the formula (7), R ₉ is either hydrogen or a C1-C6 alkyl group, M is a divalent linking group having 1 to 14 carbon atoms, k is 0 or 1, Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group, and j is 0 to Represents an integer of 5.)
[6] The polymer of [3] comprising repeating units represented by the following formula (4) and the following formula (8).

(Where R ₁₀ is hydrogen or a C1-C6 alkyl group, E is —O—, —S—, or —NH—, t is 0 or 1, and R ₁₁ is a fluoro having 1 to 18 carbon atoms. Represents an alkyl group.)
[7] A crosslinked product of the polymer according to [3] to [6].
[8] An insulating film containing at least one of the polymer according to [3] to [6] or the crosslinked product according to [7].

[9] A protective film comprising at least one of the polymer according to [4] or the crosslinked product according to [7].
[10] A liquid repellent film containing at least one of the polymer according to [6] or the crosslinked product according to [7].
[11] An organic transistor device comprising the insulating film according to [8].
[12] An organic transistor device comprising the protective film according to [9].
[13] An electronic device comprising the liquid repellent film according to [10].

Hereinafter, the present invention will be described.

The present invention is a polymerizable compound represented by the formula (1).

(In the formula (1), R ₁ represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R ₂ and R ₃ is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl One of the group consisting of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group , X represents O or S, and m represents an integer of 0 to 3.)
In the formula (1), R ₁ represents either 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 formula (1), L represents a divalent linking group having 1 to 14 carbon atoms.

The divalent linking group having 1 to 14 carbon atoms is not particularly limited as long as it is a divalent organic group that does not easily undergo structural change by radiation. For example, —CH ₂ —, —OCH ₂ —, — C (O)-, -C (O) O-, -C (O) N <, -O-, -N <,> NC (O) N <, an aryl group, and the like.

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

In the formula (1), A, R ₂ and R ₃ are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl Ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkoxy group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, 1 type of the group which consists of a cycloheteroalkyl group is represented.

In formula (1), the halogen in A, R ₂ and R ₃ is not particularly limited, and examples thereof include chlorine and fluorine.

In formula (1), the C1-C18 alkyl group in A, R ₂ and R ₃ 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. It is done.

In the formula (1), the alkoxy group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, An isobutoxy group etc. are mentioned.

In formula (1), the alkylthio group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include methylsulfanyl group, ethylsulfanyl group, isopropylsulfanyl group, n-propylsulfanyl group, n-butylsulfanyl group, isobutyl Examples thereof include a sulfanyl group and a sec-butylsulfanyl group.

In formula (1), the alkylamino group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, Examples thereof include a diethylamino group, a di (n-propyl) amino group, a methylethylamino group, and a methyl-n-propylamino group.

In the formula (1), the alkyl ketone group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, an n-butyl ketone group, and an isobutyl ketone group. And sec-butyl ketone group.

In formula (1), the alkyl ester group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a methyl ester group, an ethyl ester group, an isopropyl ester group, an n-propyl ester group, an n-butyl ester group, Examples thereof include isobutyl ester group and sec-butyl ester group.

In formula (1), the alkylamide group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, an n-butylamide group, and an isobutylamide group. And sec-butylamide group.

In formula (1), the aryl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

In formula (1), the aryl ether group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group.

In formula (1), the arylthio group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.

In formula (1), the carboxyalkyl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group. It is done.

In formula (1), the fluoroalkyl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include perfluoromethyl group, perfluoropropyl group, perfluorobutyl group, 1H, 1H-pentafluoropropyl group, 1H, 1H. , 2H, 2H-pentafluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like.

In the formula (1), the fluoroalkoxy group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H. , 2H, 2H-pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group, and the like.

In the formula (1), the fluoroalkylcarbonyl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, and 1H, 1H-pentafluoropropylcarbonyl. Group, 1H, 1H, 2H, 2H-pentafluorobutylcarbonyl group, 1H, 1H-heptafluorobutylcarbonyl group, 4,4,4-trifluorobutylcarbonyl group and the like.

In the formula (1), the fluoroalkyl ester group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a perfluoromethyl ester group, a perfluoropropyl ester group, a perfluorobutyl ester group, and a 1H, 1H-pentafluoropropyl ester. Group, 1H, 1H, 2H, 2H-pentafluorobutyl ester group, 1H, 1H-heptafluorobutyl ester group, 4,4,4-trifluorobutyl ester group and the like.

In the formula (1), the fluoroaryl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a 4-fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 1-fluoro Examples include naphthyl group, octafluoronaphthyl group, 1-fluoroanthryl group, 2-fluoroanthryl group, 9-fluoroanthryl group, 2-fluorobiphenyl group, 4-fluorobiphenyl group, and the like.

In formula (1), the fluorothio group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include perfluoromethylsulfanyl group, perfluoropropylsulfanyl group, perfluorobutylsulfanyl group, 1H, 1H-pentafluoropropylsulfanyl group, Examples thereof include 1H, 1H, 2H, 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.

In formula (1), the cycloalkyl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

In formula (1), the cycloheteroalkyl group in A, R ₂ and R ₃ is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, and tetrahydrothiophen-2-yl. 1-thiacyclohexane-4-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydrothiophen-4-yl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-2- Ir etc. are mentioned.

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

In the formula (1), m represents an integer of 0 to 3.

Another aspect of the present invention is a polymerizable compound represented by the following formula (2).

(In Formula (2), Q ₁ and Q ₂ are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1, G ₁ , G ₂ , R ₄ to R ₇ are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group _and each X 1 ~ _{X 4} are independently O or S, r and s which Independently represents an integer of 0 to 3.).

In formula (2), Q ₁ and Q ₂ represent a divalent linking group having 1 to 14 carbon atoms.

The divalent linking group having 1 to 14 carbon atoms is not particularly limited as long as it is a divalent organic group that does not easily undergo structural change by radiation. For example, —CH ₂ —, —OCH ₂ —, — And C (O) —, —C (O) O—, —C (O) N <, —O—, —N <,> NC (O) N <, and an aryl group.

In the formula (2), p and q each independently represent 0 or 1.

In formula (2), G ₁ , G ₂ and R ₄ to R ₇ are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl Ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkoxy group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl 1 type of the group which consists of group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group.

In formula (2), the halogen in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include chlorine, fluorine and the like.

In the formula (2), the C1-C18 alkyl group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Groups and the like.

In the formula (2), the alkoxy group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec -Butoxy group, isobutoxy group and the like.

In the formula (2), the alkylthio group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methylsulfanyl group, an ethylsulfanyl group, an isopropylsulfanyl group, an n-propylsulfanyl group, and n-butyl. Examples thereof include a sulfanyl group, an isobutylsulfanyl group, and a sec-butylsulfanyl group.

In formula (2), the alkylamino group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, Examples thereof include a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a methylethylamino group, and a methyl-n-propylamino group.

In the formula (2), the alkyl ketone group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, and an n-butyl ketone group. , Isobutyl ketone group, sec-butyl ketone group and the like.

In the formula (2), the alkyl ester group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methyl ester group, an ethyl ester group, an isopropyl ester group, an n-propyl ester group, an n- Examples thereof include a butyl ester group, an isobutyl ester group, a sec-butyl ester group and the like.

In formula (2), the alkylamide group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, and an n-butylamide group. , Isobutylamide group, sec-butylamide group and the like.

In the formula (2), the aryl group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

In the formula (2), the aryl ether group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group. .

In formula (2), the arylthio group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.

In the formula (2), the carboxyalkyl group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group. Groups and the like.

In the formula (2), the fluoroalkyl group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethyl group, a perfluoropropyl group, a perfluorobutyl group, and a 1H, 1H-pentafluoropropyl group. Examples thereof include 1H, 1H, 2H, 2H-pentafluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like.

In the formula (2), the fluoroalkoxy group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethoxy group, a perfluoropropoxy group, a perfluorobutoxy group, and a 1H, 1H-pentafluoropropoxy group. 1H, 1H, 2H, 2H-pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like can be mentioned.

In the formula (2), the fluoroalkyl ether group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethoxy group, a perfluoropropoxy group, a perfluorobutoxy group, and 1H, 1H-pentafluoropropoxy group. Group, 1H, 1H, 2H, 2H-pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like.

In the formula (2), the fluoroalkylcarbonyl group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, 1H, 1H— Examples thereof include a pentafluoropropylcarbonyl group, 1H, 1H, 2H, 2H-pentafluorobutylcarbonyl group, 1H, 1H-heptafluorobutylcarbonyl group, 4,4,4-trifluorobutylcarbonyl group and the like.

In the formula (2), the fluoroalkyl ester group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethyl ester group, a perfluoropropyl ester group, a perfluorobutyl ester group, 1H, 1H— Examples thereof include a pentafluoropropyl ester group, 1H, 1H, 2H, 2H-pentafluorobutyl ester group, 1H, 1H-heptafluorobutyl ester group, 4,4,4-trifluorobutyl ester group and the like.

In the formula (2), the fluoroaryl group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a 4-fluorophenyl group and a 2,3,4,5,6-pentafluorophenyl group. 1-fluoronaphthyl group, octafluoronaphthyl group, 1-fluoroanthryl group, 2-fluoroanthryl group, 9-fluoroanthryl group, 2-fluorobiphenyl group, 4-fluorobiphenyl group, and the like.

In the formula (2), the fluorothio group in G ₁ , G ₂ , R ₄ to R ₇ is not particularly limited, and examples thereof include a perfluoromethylsulfanyl group, a perfluoropropylsulfanyl group, a perfluorobutylsulfanyl group, and 1H, 1H-pentafluoro. Examples thereof include a propylsulfanyl group, 1H, 1H, 2H, 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.

In formula (2), the cycloalkyl group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

In the formula (2), the cycloheteroalkyl group in G ₁ , G ₂ and R ₄ to R ₇ is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, tetrahydrothiophene. -2-yl, 1-thiacyclohexane-4-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydrothiophen-4-yl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydro And pyran-2-yl.

In formula (2), X ₁ to X ₄ each independently represents O or S.

In formula (2), r and s each independently represent an integer of 0 to 3.

In addition, the present invention includes at least one of the following formulas (3) to (5) obtained by using the polymerizable compound represented by the above formula (1) or the above formula (2) as a repeating unit, And it is a polymer containing at least 1 type of repeating unit of the group which consists of the following formula | equation (6) thru | or Formula (8).

(In Formula (3) and Formula (4), R ₁ represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, A, R ₂ and R ₃ are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group , Aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cyclo One of the group consisting of heteroalkyl groups, X represents O or S, and m represents an integer of 0 to 3. .)

(In formula (8), R ₁₀ represents hydrogen or a C1-C6 alkyl group, E represents —O—, —S—, or —NH—, t represents 0 or 1, and R ₁₁ represents 1 to Represents 18 fluoroalkyl groups.)
The present invention is preferably a polymer containing repeating units represented by the following formulas (4) and (6). Thereby, the polymer of this invention can be used more suitably as an insulating film or a protective film.

(In the formula (4), R ₁ to R ₃ , A, L, X, m and n are the same as those defined in the formula (1)).

The repeating body represented by the formula (6) in the polymer of the present invention will be described.

(In formula (6), R ₈ represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.)
In the formula (6), R ₈ represents hydrogen or a C1-C6 alkyl group.

In the formula (6), the C1-C6 alkyl group in R ₈ 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 (6), Z represents a C1-C12 alkyl group.

In formula (6), the C1-C12 alkyl group in Z 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 polymer of the present invention is preferably a polymer including at least one of the following formulas (3) to (5) as a repeating unit and including a repeating unit represented by the formula (7).

(In the formula (7), R ₉ is either hydrogen or a C1-C6 alkyl group, M is a divalent linking group having 1 to 14 carbon atoms, k is 0 or 1, Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group, and j is 0 to Represents an integer of 5.)
The polymer of the present invention preferably contains at least one of the above formulas (3) to (5) as a repeating unit.

The polymer of the present invention preferably contains at least repeating units of the above formulas (3) and (7).

The polymer of the present invention preferably contains at least a repeating unit of the above formula (4).

The polymer of the present invention preferably contains a repeating unit of the above formula (7).

The polymer of the present invention includes a polymer containing the above formula (4) and the above formula (7) as repeating units, a polymer containing the above formula (5) and the above formula (7) as repeating units, and the above formula (4). It is preferably one of the group consisting of polymers containing the above formulas (5) and (7) as repeating units, and more preferably a polymer containing the above formulas (4) and (7) as repeating units. It is a coalescence. Thereby, it is possible to crosslink by irradiation with short radiation, and the insulation performance of the obtained crosslinked body is improved.

The ratio of the repeating units of the above formulas (4), (5) and (7) is not particularly limited, and can be appropriately determined depending on the balance between solubility in an organic solvent and crosslinkability by ultraviolet rays. For example, from the viewpoint of solubility in a general-purpose organic solvent, when the total number of repeating units of formulas (4), (5) and (7) is 100 mol%, the repeating unit represented by formula (7) It is preferable that the ratio of is 40 mol% or more.

The repeating body represented by the formula (7) in the polymer of the present invention will be described.

In the formula (7), R ₉ represents hydrogen or a C1-C6 alkyl group.

The C1-C6 alkyl group for R ₉ in formula (7) 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 formula (7), M is not particularly limited as a divalent linking group having 1 to 14 carbon atoms. For example, —C (O) O—, —OC (O) —, —C (O) OCH ₂ —, —CH ₂ —, —C (O) —, —O—, —OCH ₂ CH ₂ O— and the like can be mentioned.

In the formula (7), k represents 0 or 1.

In formula (7), each Y is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group. , Aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkoxy group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, cyclo 1 type of the group which consists of heteroalkyl groups is represented.

In formula (7), the halogen in Y is not particularly limited, and examples thereof include chlorine and fluorine.

In formula (7), the C1-C18 alkyl group in Y 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 formula (7), the alkoxy group in Y is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and an isobutoxy group. .

In formula (7), the alkylthioether group in Y is not particularly limited, and examples thereof include methylsulfanyl group, ethylsulfanyl group, isopropylsulfanyl group, n-propylsulfanyl group, n-butylsulfanyl group, isobutylsulfanyl group, sec- A butylsulfanyl group etc. are mentioned.

In formula (7), the alkylamino group in Y is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, a diethylamino group, a di (n -Propyl) amino group, methylethylamino group, methyl-n-propylamino group and the like.

In formula (7), the alkyl ketone group in Y is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, an n-butyl ketone group, an isobutyl ketone group, and a sec-butyl ketone group. Is mentioned.

In formula (7), the alkyl ester group in Y is not particularly limited. For example, methyl ester group, ethyl ester group, isopropyl ester group, n-propyl ester group, n-butyl ester group, isobutyl ester group, sec- A butyl ester group etc. are mentioned.

In formula (7), the alkylamide group in Y is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, an n-butylamide group, an isobutylamide group, and a sec-butylamide group. Is mentioned.

In formula (7), the aryl group in Y is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.

In formula (7), the aryl ether group in Y is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group.

In formula (7), the arylthioether group in Y is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.

In formula (7), the carboxyalkyl group in Y is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group.

In formula (7), the fluoroalkyl group in Y is not particularly limited, and examples thereof include perfluoromethyl group, perfluoropropyl group, perfluorobutyl group, 1H, 1H-pentafluoropropyl group, 1H, 1H, 2H, 2H-penta. A fluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like can be mentioned.

In formula (7), the fluoroalkoxy group in Y is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H, 2H, 2H-penta. Examples thereof include a fluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like.

In formula (7), the fluoroalkyl ether group in Y is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H, 2H, 2H— A pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like can be mentioned.

In formula (7), the fluoroalkylcarbonyl group in Y is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, a 1H, 1H-pentafluoropropylcarbonyl group, 1H, 1H, Examples include 2H, 2H-pentafluorobutylcarbonyl group, 1H, 1H-heptafluorobutylcarbonyl group, 4,4,4-trifluorobutylcarbonyl group, and the like.

In formula (7), the fluoroalkyl ester group in Y is not particularly limited, and examples thereof include perfluoromethyl ester group, perfluoropropyl ester group, perfluorobutyl ester group, 1H, 1H-pentafluoropropyl ester group, 1H, 1H, Examples include 2H, 2H-pentafluorobutyl ester group, 1H, 1H-heptafluorobutyl ester group, 4,4,4-trifluorobutyl ester group and the like.

In formula (7), the fluoroaryl group in Y is not particularly limited, and examples thereof include 4-fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 1-fluoronaphthyl group, and octafluoronaphthyl. Group, 1-fluoroanthryl group, 2-fluoroanthryl group, 9-fluoroanthryl group, 2-fluorobiphenyl group, 4-fluorobiphenyl group, and the like.

In formula (7), the fluorothioether group in Y is not particularly limited, and examples thereof include perfluoromethylsulfanyl group, perfluoropropylsulfanyl group, perfluorobutylsulfanyl group, 1H, 1H-pentafluoropropylsulfanyl group, 1H, 1H, 2H. , 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.

In formula (7), the cycloalkyl group in Y is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

In formula (7), the cycloheteroalkyl group in Y is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, tetrahydrothiophen-2-yl, 1-thiacyclohexane- Examples include 4-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydrothiophen-4-yl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-2-yl and the like.

In formula (7), j represents an integer of 0 to 5.

The polymer of the present invention preferably contains a repeating unit represented by the following formula (4) and the following formula (8).

(Where R ₁₀ is hydrogen or a C1-C6 alkyl group, E is —O—, —S—, or —NH—, t is 0 or 1, and R ₁₁ is a fluoro having 1 to 18 carbon atoms. Represents an alkyl group.)
The repeating body represented by Formula (8) in the polymer of the present invention will be described.

In the formula (8), R ₁₀ represents hydrogen or a C1-C6 alkyl group.

The C1-C6 alkyl group for R ₁₀ in formula (8) 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 (8), E represents —O—, —S—, or —NH—.

In the formula (8), k represents 0 or 1.

In the formula (8), R ₁₁ represents a fluoroalkyl group having 1 to 18 carbon atoms.

In formula (8), the fluoroalkyl group for R ₁₁ is not particularly limited, and examples thereof include 2,2,2-trifluoroethyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1 1,1,2,2-pentafluorobutyl group, 1,1,1,2,2-pentafluoropentyl group, 1,1,1,2,2,3,3-heptafluorohexyl group, 1,1, Examples include 1,2,2,3,3-heptafluoroheptyl group, 1,1,1,2,2,3,3-heptafluorooctyl group, hexafluoroisobutyl group and the like.

The polymerizable compound represented by the formulas (1) and (2) of the present invention has a benzopyran group that is a photocrosslinkable functional group. Therefore, a copolymer (polymer) obtained by copolymerizing the polymerizable compound with another polymerizable compound has photocrosslinkability, and the photocrosslinkability depends on the amount of the polymerizable compound introduced. It changes depending on. In addition to this, the polymerizable compound represented by the formula (1) of the present invention has a feature that the influence on the solubility in a lower alcohol is small. When the polymerizable compound according to the present invention is used, A copolymer (polymer) excellent in both solubility in a lower alcohol can be obtained.

The polymerizable compound represented by the formulas (1) and (2) of the present invention is suitably used as a polymer obtained by polymerization using the polymerizable compound as a monomer. At this time, in the polymer, the polymerizable compound represented by the formula (1) is a repeating unit represented by the formula (4), and the polymerizable compound represented by the formula (2) is represented by the formula (5). It becomes a repeating unit represented by.

In the present invention, the repeating unit represented by the formula (4) is a photocrosslinking group, and the content thereof is shortening of the photocrosslinking time, high crosslink density (excellent solvent resistance), and dissolution in a lower aliphatic alcohol. From the viewpoint of properties, when the total of repeating units of formulas (6) and (4) is 100 mol%, the ratio of the repeating units represented by formula (4) is preferably 5 to 35 mol%. .

When M is the number of the longest carbon chains constituting L in the formula (4), it is more preferable to complete photocrosslinking in a short time. Therefore, this M constitutes Z in the formula ((6)) It is preferable that N + 2 ≧ M ≧ N−2 is satisfied with respect to the number N of the longest carbon chains.

As another aspect of the polymer of the present invention, the polymer containing at least one of the above formula (4) and formula (5) as a repeating unit and containing a repeating unit represented by formula (7) is crosslinked. The polymer which performed can be shown.

Radiation is preferably used for the crosslinking treatment. Examples of radiation include ultraviolet rays having a wavelength of 245 to 350 nm. The amount of radiation irradiation is appropriately changed depending on the composition of the polymer, and examples thereof include 100 to 500 mJ / cm ² , and further 100 to 300 mJ / cm ^2, which prevents a reduction in the degree of crosslinking and shortens the process. In order to improve the economic efficiency due to time, it is preferably 50 to 300 mJ / cm ² and 50 to 200 mJ / cm ² . The environment in particular when irradiating an ultraviolet-ray is not restrict | limited, It can carry out in air | atmosphere, inert gas, or a fixed amount of inert gas flow.

Whether the copolymer is cross-linked can be determined by the solubility when the copolymer film is immersed in a good solvent, and the degree of cross-linking can be quantitatively evaluated by measuring the residual film rate described later. Specifically, if the copolymer thin film formed on the glass plate is immersed in a good solvent without being crosslinked, the copolymer film is completely dissolved. On the other hand, a sufficiently crosslinked copolymer film does not dissolve in a good solvent, maintains a solid state, and does not change the thickness of the film. In addition, when the crosslinking is insufficient, the polymer film maintains a solid state, but a part of the copolymer is dissolved, so that the film thickness becomes small. Therefore, it is possible to quantitatively determine how much the copolymer has been crosslinked by measuring the film thickness before and after the solvent immersion. The structure of the polymer after the crosslinking treatment can be identified by a method using a thermogravimetric / mass spectrometer (TG-MS) and an infrared absorption spectrum (IR).

In the present invention, there is no limitation on the molecular weight of the polymer containing at least one repeating unit of the group consisting of the above formulas (3) to (8), for example, 5000 to 1,000,000 (g / mol). Etc. From the viewpoint of the solution viscosity of the polymer and the mechanical strength, it is preferably 10,000 to 500,000 (g / mol).

The polymer of the present invention can be obtained by polymerizing the monomers represented by the above formulas (1) and (9) by a known radical polymerization method.

(In formula (9), R ₈ and Z are the same as defined in formula (6)).

The polymer of the present invention can be obtained by polymerizing at least one monomer of the formula (1) or the formula (2) and a monomer represented by the formula (10) by a radical polymerization method. it can.

(In the formula (10), R ₉ , M, Y, k and j are the same as those defined in the formula (7)).

The polymer of the present invention can be obtained by polymerizing the monomers represented by the above formulas (1) and (11) by a known radical polymerization method.

(In formula (11), R ₁₀ , R ₁₁ , E, and t are the same as those defined in formula (8).)
In the present invention, specific examples of the polymerizable compound represented by the formula (1) include the following in addition to 7-methacryloyloxy-4-oxobenzopyran represented by the formula (12). It is done.

In the present invention, specific examples of the monomer represented by the formula (2) include the following compounds.

In the polymerizable compound of the present invention, at least one monomer of the group consisting of the monomer represented by [Chemical Formula 33] and the monomer represented by [Chemical Formula 36 to Chemical Formula 56] is polymerized. It is preferable. As a result, it is dissolved in a lower aliphatic alcohol, photocrosslinked in a short time with ultraviolet rays, and becomes a polymer for forming an insulating layer capable of forming a contact hole.

The polymerizable compound represented by the formula (1) of the present invention can be produced by a known method in which a benzopyran compound having a hydroxy group and an acid chloride are reacted in a solvent. As the acid chloride, acryloyl chloride, methacryloyl chloride, 2-alkyl acryloyl chloride, or 2-alkyl methacryloyl chloride is used, and the molar ratio of acid chloride to the benzopyran compound is reduced to reduce the amount of unreacted acid chloride. .5 to 1.0 is preferable. Solvents that can be used in this reaction dissolve the above-mentioned benzopyran compound and acid chloride, do not react with these compounds, and are not limited as long as they are sufficiently dehydrated. For example, tetrahydrofuran, methylene chloride, toluene, etc. Can be used. In this reaction, in order to increase the reaction rate and increase the yield, an acid acceptor for hydrogen chloride generated in the reaction and an esterification catalyst, and a polymerization inhibitor for preventing polymerization of a polymerizable compound during the reaction. Is preferably added. Examples of the acid acceptor include dehydrated triethylamine and pyridine, examples of the catalyst include strong bases such as N, N-dimethyl-4-aminopyridine, and examples of the polymerization inhibitor include hydroquinone and dibutylhydroxytoluene. The The reaction temperature is not particularly limited, but is preferably 0 to 60 ° C. in order to prevent polymerization reaction. The reaction time is not particularly limited, but is preferably 2 to 6 hours because of excellent economic efficiency.

Further, the polymerizable compound represented by the formula (1) of the present invention can also be produced using a known method. For example, 6-vinyl-4-oxo-benzopyran compound, or 7-vinyl-4-oxo-benzopyran compound starts from 6-methyl-4-oxo-benzopyran compound, or 7-methyl-4-oxo-benzopyran compound Raw material, a step of bromomethylating a methyl group using a carbon tetrachloride as a solvent and a radical generator such as N-bromosuccinimide, a peroxide compound, or azoisobutyronitrile, a bromomethyl group as a solvent and a dimethylsulfoxide as a solvent The catalyst can be used for the formylation with sodium hydrogencarbonate, and the formyl group can be produced by four processes for vinylation with potassium tert-butoxide using methyltriphenylphosphonium bromide as a catalyst.

The polymerizable compound represented by the formula (2) of the present invention can be produced by a known method in which a benzopyran compound having a hydroxy group and an acid chloride are reacted in a solvent. Examples of the acid chloride include acid chlorides such as fumaric acid dichloride and maleic acid dichloride. The molar ratio of the acid chloride to the benzopyran compound is preferably 0.35 to 0.45 in order to reduce the amount of unreacted acid chloride. The solvent that can be used in this reaction is not limited as long as it dissolves the above-mentioned benzopyran compound and acid chloride, does not react with these compounds, and is sufficiently dehydrated. For example, N, N-dimethylacetamide, An amide solvent such as N-methylpyrrolidone can be used. In this reaction, in order to increase the reaction rate and increase the yield, an acid acceptor for hydrogen chloride generated in the reaction and an esterification catalyst, and a polymerization inhibitor for preventing polymerization of a polymerizable compound during the reaction. Is preferably added. Examples of the acid acceptor include dehydrated triethylamine and pyridine, examples of the catalyst include strong bases such as N, N-dimethyl-4-aminopyridine, and examples of the polymerization inhibitor include hydroquinone and dibutylhydroxytoluene. The The reaction temperature is not particularly limited, but is preferably 0 to 70 ° C. in order to prevent the polymerization reaction. The reaction time is not particularly limited, but is preferably 2 to 6 hours because of excellent economic efficiency.

In the present invention, specific examples of the monomer represented by the formula (10) include styrene, α-methylstyrene, 2-chlorostyrene, 2-bromostyrene, 2-fluorostyrene, 3-chlorostyrene, 3-bromostyrene, 3-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-fluorostyrene, 4-chloromethylstyrene, 3,5-trifluoromethylstyrene, 4-trifluorostyrene, 2,3, 4,5,6-pentafluorostyrene may be mentioned.

In the present invention, specific monomers represented by the formula (11) include, in addition to 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate represented by the formula (13), for example, the following: Can be mentioned.

When radically copolymerizing the monomer represented by the above formula (1) or (2) and the monomer represented by at least one selected from the group consisting of the formulas (9) to (11), For the radical copolymerization, known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be used.

The solvent used in the solution polymerization is not limited as long as the above-described monomer and the polymer of the present invention are dissolved. For example, amide solvents such as dimethylformamide and dimethylacetamide; toluene, xylene, 1,3-bis Aromatic hydrocarbon solvents such as (trifluoromethyl) benzene and α, α, α-trifluoromethylbenzene; cyclic ethers such as tetrahydrofuran and tetrahydropyran, and the like. These solvents can also be used in combination. At this time, the polymerization temperature is selected depending on the initiator used, but is not particularly limited. As the initiator, any of azo initiators such as azoisobutyronitrile; peroxide initiators such as benzoyl peroxide and di (t-butyl) peroxide can be used. The reaction time is set according to the half-life of the initiator used and is not limited at all, but is preferably 4 to 8 hours from the viewpoint of economy.

The polymer of the present invention can be applied or printed on various substrates in a solution state dissolved in a solvent. The solvent can be used without any limitation as long as it dissolves the polymer and at the same time does not dissolve the organic semiconductor used in the production of the organic transistor. For example, methanol, ethanol, n-propanol, isopropanol, 1- Aliphatic alcohols such as butanol, 2-butanol, t-butanol, n-pentanol; chlorinated aliphatic hydrocarbon compounds such as methylene chloride and 1,1,2-trichloroethylene; dibutyl ether, diisobutyl ether, tetrahydrofuran, tetrahydro Ethers such as pyran and dioxane; cyclohexane, benzene, toluene, xylene, cumene, mesitylene, ethylbenzene, isopropylbenzene, N-hexylbenzene, tetralin, decalin, 1,3-bis (trifluoromethyl) benzene, , Α, α-trifluoromethylbenzene, α, α, α, α ', α', α'-hexafluoro-m-xylene and other aromatic hydrocarbons; halogenated chlorobenzene, dichlorobenzene, bromobenzene and the like Aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclopentanone, cyclohexanone; ethyl acetate, dimethyl phthalate, methyl salicylate, amyl acetate n-butyl acetate, isobutyl acetate, propyl propionate , Esters such as dimethyl phthalate, methyl salicylate, amyl acetate, amides such as N-methylpyrrolidone, dimethylformamide; diethylene glycol butyl methyl ether, diethylene glycol dimethyl ether, diethyl Glycols such as ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, 1-nitropropane, carbon disulfide, limonene, etc. may be used alone or in combination of two or more solvents . Among these, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, t-butanol, n-pentanol and the like can be applied on the organic semiconductor layer. Are preferred, and lower aliphatic alcohols having 4 or less carbon atoms are more preferred.

There are no restrictions on the coating or printing method, such as 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, Printing can be performed using gravure printing, flexographic printing, screen printing, inkjet printing, letterpress reverse printing, and the like.

In addition, when using the polymer of this invention as an insulating layer, since this insulating layer is formed using these coating or printing methods, this insulating layer needs the solubility with respect to said solvent. . When a fluorine-containing monomer represented by the formula (10) and having a specific structure such as 2,3,4,5,6-pentafluorostyrene is used, the polymer of the present invention is soluble in a general-purpose solvent. However, it also dissolves in fluorinated solvents. For this reason, the polymer of the present invention is dissolved in a fluorine-based solvent such as hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene and printed on the uppermost layer of the organic transistor element as a protective film. You can also. It can also be used as an insulating film that can be printed on the organic semiconductor layer in the top gate type transistor element.

The polymer according to the present invention has a photocrosslinkable group, and radiation is suitably used for the photocrosslinking (photocyclization). Examples of the radiation include ultraviolet rays having a wavelength of 245 to 350 nm. The irradiation amount of radiation is appropriately changed depending on the composition of the polymer. For example, it is 100 to 500 mJ / cm ^{2, and it} is possible to prevent a decrease in the degree of crosslinking and improve economy by shortening the process. It is preferably 50 to 300 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, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds, and the like, and benzophenone compounds having high compatibility with the polymer used in the present invention are preferable. The sensitizers can be used in combination of two or more as required.

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

Further, the polymer of the present invention contains a compound containing a plurality of olefins such as ethylene and propylene as a crosslinking agent in one molecule as a crosslinking agent in order to increase the crosslinking density or shorten the crosslinking time; A compound containing a plurality of cyclic olefins such as cyclopentene in one molecule may be blended. These compounds may be used alone or in combination of two or more.

In addition, the polymer of the present invention can be efficiently photocrosslinked in a short time, and in order to efficiently photocrosslink in a shorter time, the time required for photocrosslinking is preferably within 2 minutes. In addition, since it is suitable for control of crosslinking time, it is more preferable that the time required for crosslinking is within 1 minute.

In the present invention, specific examples of the monomer represented by the formula (1) include the following in addition to 6- (chromone-7-oxy) hexamethyl methacrylate represented by the formula (14). It is done.

The polymer of the present invention can be suitably used as an insulating film containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention. In addition, the polymer of the present invention can be suitably used as an organic transistor device including the insulating film.

The polymer of the present invention can be suitably used as a protective film containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention. Moreover, the polymer of this invention can be used suitably as an organic transistor device containing this protective film.

The polymer of the present invention can be suitably used as a liquid repellent film (layer) containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention. The polymer of the present invention can be suitably used as an electronic device including the liquid repellent film, particularly as an organic transistor device.

When the polymer of the present invention is used in an organic transistor device (hereinafter referred to as “organic transistor”), the organic transistor of the present invention has a bottom gate-top contact type (A), bottom gate-bottom contact type (A) shown in FIG. B), top gate-top contact type (C), and top gate-bottom contact type (D) may be used. The polymer of the present invention has particularly high applicability to devices in the forms of (C) and (D). Here, 1 is an organic semiconductor layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

When the polymer of the present invention is used as a protective layer (film) for the organic semiconductor layer, the polymer can be used in either an uncrosslinked state or a crosslinked state.

In the organic transistor, a substrate (substrate) that can be used is not particularly limited as long as sufficient flatness capable of producing an element can be ensured. For example, glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, Inorganic material substrates such as tantalum pentoxide and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated papers; A material obtained by multilayering these materials 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.

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 it can also be used as a bipolar transistor that combines N-type and P-type. Moreover, both low molecular and high molecular organic semiconductors can be used, and these can also be mixed and used. Specific examples of the compound include formulas (F-1) to (F-11).

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, but the viewpoint of forming a more uniform semiconductor layer and reducing the thickness of the layer Therefore, it 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, 3-methoxybutyl acetate, cyclohexanol Acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol Diacetate, ethyl acetate Tate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3 -Dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran Examples include 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N, N-dimethylformamide, N-methyl-2-pyrrolidone, limonene, and the like. In order to obtain a film, a solvent having a high solubility of an organic semiconductor and a boiling point of 100 ° C. or more is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole. Pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. Moreover, the mixed solvent which mixed 2 or more types of the above-mentioned solvent in the appropriate ratio can also be used.

The organic transistor of the present invention can be suitably used as an organic transistor having contact holes formed by etching. At this time, the solvent used for etching at the time of contact hole formation is not limited as long as it is a solvent that dissolves the polymer of the present invention and the organic semiconductor to be used. For example, toluene, xylene, ethylbenzene, 1,2,4-trimethyl Benzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxy Examples include general-purpose aromatic hydrocarbon solvents such as benzene and 1,3-dimethoxybenzene. If the above conditions are satisfied, a mixed solvent in which two or more of these solvents are mixed 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.

Examples of a gate electrode, a source electrode, or a drain electrode that can be used in the present invention include aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, Examples include conductive materials such as inorganic electrodes such as platinum, titanium, tantalum, graphene, and carbon nanotubes, or organic electrodes such as doped conductive polymers (for example, PEDOT-PSS). It can also be used by laminating. Moreover, in order to raise the injection | pouring efficiency of a carrier, surface treatment can also be implemented using a surface treating agent for these electrodes. Examples of such a surface treatment agent include benzenethiol and pentafluorobenzenethiol.

In addition, there is no particular limitation on the method for forming the electrode on the substrate, the insulating layer, or the organic semiconductor layer, and examples thereof include vapor deposition, high-frequency sputtering, electron beam sputtering, and the like. Methods such as solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, ink jet printing, letterpress reverse printing, etc., using ink dissolved in an organic solvent Can also be adopted.

During electrode formation (circuit pattern formation), the surface of the insulating layer is increased by irradiating the surface of the insulating layer with vacuum ultraviolet (VUV) light after UV crosslinking of the insulating layer and using a light shielding mask. Thus, the wettability with respect to the organic solvent can be increased. The irradiation time of VUV light varies depending on the structure of the polymer used in the insulating layer to be used and the distance between the light source and the surface of the insulating layer, but is preferably 1 minute to 8 minutes, more preferably 1 minute to 5 minutes from the viewpoint of economy. Minutes.

The mobility of the organic transistor of the present invention is preferably 0.20 cm ² / Vs or more from the viewpoint of practicality of the organic transistor element.

The organic transistor of the present invention preferably has a threshold voltage of -10.0 V or higher and lower than 0 V from the viewpoint of practicality of the organic transistor element.

The organic transistor of the present invention preferably has a leakage current density of 10 ⁻⁹ A / cm ² or less from the viewpoint of practicality of the organic transistor element.

According to the present invention, it is possible to provide a polymer for forming an insulating layer which can be dissolved in a lower aliphatic alcohol and photocrosslinked in a short time with ultraviolet rays to form a contact hole.

According to the present invention, it is possible to provide a polymer that dissolves in a general-purpose solvent, crosslinks at room temperature in a short time, and has excellent insulating properties.
ADVANTAGE OF THE INVENTION According to this invention, the polymer which is soluble in a solvent, photocrosslinks in normal temperature for a short time, insolubilizes in a solvent, and shows liquid repellency can be provided.

; It is a figure which shows the cross-sectional shape of an organic transistor. FIG. 2 is a view showing a ¹ H-NMR chart of a polymerizable compound produced in Example 1. FIG. 2 is a diagram showing a ¹³ C-NMR chart of a polymerizable compound produced in Example 1. FIG. 2 is a diagram showing a ¹ H-NMR chart of a polymerizable compound produced in Example 2. FIG. 2 is a diagram showing a ¹ H-NMR chart of a polymerizable compound produced in Example 3. FIG. 2 is a diagram showing a ¹ H-NMR chart of a polymerizable compound produced in Example 4. FIG. 3 is a view showing a ¹ H-NMR chart of polymer 1 produced in Example 5. FIG. 2 is a diagram showing a ¹ H-NMR chart of polymer 6 produced in Example 10. FIG. 2 is a view showing a ¹ H-NMR chart of polymer 7 produced in Example 11. FIG. 3 is a view showing a ¹ H-NMR chart of polymer 8 produced in Example 12. FIG. 2 is a view showing a ¹ H-NMR chart of polymer 12 produced in Example 15.

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. 7-Hydroxy-4-oxo-benzopyran (7HOB) was synthesized by the method described in Journal of Heterocyclic Chemistry, 2015, 52, 562 pages. Hexane, ethyl acetate, ethanol, carbon tetrachloride, dimethyl sulfoxide, sodium bicarbonate, N-methylpyrrolidone, methanol, isopropanol, dimethylformamide (DMF), dehydrated pyridine, tetrahydrofuran (THF), dehydrated tetrahydrofuran (THF), toluene, styrene Azoisobutyronitrile (AIBN) is a reagent manufactured by Wako Pure Chemical Industries, Ltd., dibutylhydroxytoluene (BHT), 4-dimethylaminopyridine, 2,3,4,5,6-pentafluorostyrene (PFS), and Methacryloyl chloride, pentafluorobenzenethiol, N-bromosuccinimide, trimethyltriphenylphosphonium bromide, and potassium-t-butoxide are reagents manufactured by Tokyo Chemical Industry, and are used for silica gel column chromatography. The manufacturing of Kiesel-Gel-60, poly (n- butyl acrylate), polyvinyl butyral, and poly (vinyl alcohol) is with a reagent manufactured by Sigma-Aldrich. Poly (n-octyl methacrylate) was synthesized according to the method described in Polymer Science, Series B, 2016, Vol. 58, No. 6, page 675. A product Cytop manufactured by AGC Asahi Glass Co., Ltd. was used for the fluorine-based cyclic ether polymer, and perfluorotributylamine (CYTOP CT-SOLV180 manufactured by AGC Asahi Glass Co., Ltd.) was used as the solvent for Cytop.

7-Methyl-4-oxo-benzopyran was prepared according to the method described in Journal of Heterocyclic Chemistry, Vol. 52, No. 2, 562, 2015. 7-formyl-4-oxo-benzopyran is described in Journal of Organic Chemistry, Vol. 58, No. 26, p. 598, 1993, by the method described in Medical Chemistry, Vol. 44, 672, 2001. 7-vinyl-4-oxo-benzopyran was prepared by the method described in Journal of American Chemical Society, Vol. 126, No. 12, p. 3856, 2004.

In Examples, NMR, polymer solubility, filterability, spin coating, film thickness measurement, UV irradiation, vacuum deposition, residual film rate, contact angle, surface tension, dielectric breakdown strength, dispenser printing, partition wall formation, The evaluation of the organic transistor element was carried out under the following conditions / apparatus.
<NMR>
JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.) was used for measurement using a polymer deuterated chloroform solvent.

In Examples 5 to 9, the content of benzopyran groups was calculated using ¹ H-NMR by the following method.

X = a (I ₁ + I ₂ ) / {a (I ₁ + I ₂ ) + bI ₃ }
(Where I ₁ represents the peak intensity at δ 8.0 to 8.3 ppm, I ₂ represents the peak intensity at δ 6.0 to 6.5 ppm, and I ₃ represents the peak intensity at δ 3.3 to 4.1 ppm, a represents the number of hydrogen atoms bonded to the carbon adjacent to the ester group in the substituent Z of the formula (6), and b represents the total number of hydrogen atoms of the substituents R ₂ and R ₃ of the benzopyran group in the formula (4). Represents.)
In Examples 10 to 14, the benzopyran group content X was calculated by the following method using ¹ H-NMR according to the following formula.
X = (3I ₂ −aI ₁ ) / {(5-a) I1 + 2I ₂ }
(Where I ₁ is the peak intensity at δ 0.8 to 2.5 ppm, I ₂ is the peak intensity at δ 6.0 to 8.5 ppm, and a is bonded to the phenyl group in formula (4) or (5). This represents the number of hydrogen atoms.)
In Examples 15 to 17, a polymer solution prepared by dissolving a polymer in α, α, α, α ′, α ′, α′-hexafluoro-m-xylene (HFMX) was placed in an inner tube, The measurement was performed using a double tube in which deuterated chloroform was put in the outer tube. Note that the three peaks of δ 7.68 ppm, δ 7.50 ppm, and δ 7.28 ppm appearing in the NMR spectrum are due to the hydrogen of the aromatic ring of HFMX.

The content X of the chromone group was calculated by the following formula using ¹ H-NMR.

X = (4α−13) / (6 + 2α)
(Here, α = I ₁ / I ₂ , I ₁ represents a peak integral value of δ3.0 to δ1.0 ppm, and I ₂ represents a peak integral value of δ4.5 to δ3.8 ppm.)
<Spin coat>
MS-A100 manufactured by Mikasa Corporation was used.
<Film thickness measurement>
Measurements were made using a Bruker DektakXT stylus profiler.
<UV irradiation>
Using UV-System and CSN-40A-2 manufactured by GS Yuasa Corporation, the UV irradiation time was adjusted by changing the conveyance speed under the condition of UV intensity of 4.0 kW / cm ² .
<Vacuum deposition>
A small vacuum deposition apparatus VTR-350M / ERH manufactured by ULVAC KIKOH Co., Ltd. was used.
<Polymer solubility>
When the test solvent was toluene, xylene, mesitylene, and tetralin, it was evaluated as “dissolved” when dissolved in any of these organic solvents, and “insoluble” when not dissolved in any of the solvents.
<Filterability>
When 2ML of the solution obtained by dissolving the polymer in the test solvent so as to have a concentration of 5 wt% is filtered through a Teflon (registered trademark) filter having a pore size of 0.22 μm, and there is no increase in filtration pressure and clogging. “Good” and other cases were evaluated as “bad”.
<Residual film rate (solvent resistance)>
A polymer solution is spin-coated on a cleaned and dried 30 × 30 mm ² glass (Corning Eagle XG) using a spin coater so that the film thickness after drying is 500 nm, and is sufficiently dried. I let you. This insulating film was irradiated with 300 mJ / cm ² of ultraviolet rays to photocrosslink the insulating film. The thickness of this film was measured by Bruker DektakXT stylus profiler and a _{T 0.} Then, 1 minute after immersion in a good solvent I ~ III of the glass plate the photocrosslinked insulating film is coated toluene, or the polymer, evaporate the toluene at room temperature was taken out, T ₁ and measure the thickness It was. Using these measured film thicknesses, the remaining film ratio was calculated by the following equation.

Remaining film ratio = T ₁ / T ₀ × 100 (%)
Here, as the good solvents I to III of the polymer, 1,3-bis (trifluoromethyl) benzene (solvent I, a reagent manufactured by Tokyo Chemical Industry), tris (nonafluorobutyl) amine (solvent II, Fluorinert (manufactured by 3M Japan) ( (Trademark) FC-43) and di-nonafluorobutyl-pentafluoroethylamine (solvent III, CT-Solvent (trademark) -180 manufactured by Asahi Glass).

The lower the remaining film ratio, the less photocrosslinking and the poor solvent resistance. When the remaining film ratio is 0%, the film is completely dissolved.
<Contact angle and surface tension>
When the surface tensions of the liquid and the substrate are γ _L and γ _S , respectively, when γ _L > γ _S , the liquid is repelled by the substrate and the contact angle θ becomes large (for example, contact angle θ ≧ 60). On the other hand, when γ _L <γ _S , the liquid spreads on the substrate and the contact angle θ becomes small (for example, the contact angle θ <50).

The contact angle was measured using a contact angle meter drop master DM300 manufactured by Kyowa Interface Science Co., Ltd. The surface tension γ _{s of the} polymer was determined according to the following procedures (1) to (3).
(1) The contact angle θ between a polymer film formed by spin-coating a polymer on glass, water, and diiodomethane was measured.
(2) The dispersion term (γ _S ^d ) and the polar term (γ _S ^p ) of the surface tension of the polymer film were determined from the obtained contact angle θ using the following formula.

(Where θ is the contact angle, γ _L , γ _L ^d , and γ _L ^p are the surface tension of the measurement solvent, the surface tension dispersion term, and the surface tension polarity term, γ _S , γ _S ^d , and gamma _S ^p represents the surface tension of the polymer film, the surface tension dispersion terms, and a polar term of the surface tension.)
(3) The surface tension γ _S of the polymer film was determined from γ _S ^d and γ _S ^p by the following formula.

<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 polymer (insulator) is formed on the substrate on which the electrode is formed, and a gold electrode is vacuum-deposited on the polymer film to produce a MIM (Metal Insulator Metal) capacitor. A voltage was applied between the electrodes, and a voltage at which a current began to flow inside the dielectric layer due to dielectric breakdown was measured. A value divided by the thickness of the polymer film was taken as dielectric breakdown strength.
<Dispenser printing>
An IMAGE MASTER 350PC SMART manufactured by Musashi Engineering Co., Ltd. was used.
<Formation of partition walls>
A mask (partition forming mask) obtained by patterning 10 square × 10 micron squares 10 × 10 cm in a 10 cm × 10 cm square with 10 in a row and 10 in a horizontal pattern was used. A mask is placed on a polymer film having a thickness of 100 nm printed on a substrate, irradiated with 100 mJ / cm ² of ultraviolet rays, and then uncrosslinked parts are washed and removed with a good solvent of the polymer to thereby remove 50 on the film. A partition wall having a shape of 100 holes of × 50 μm ² size was formed.
<Evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type element or a bottom gate / bottom contact (BGBC) type element, which is one form of an organic field effect transistor, is manufactured, and source-drain is used using a semiconductor parameter analyzer SCS4200 manufactured by Keithley The mobility, threshold voltage, and leakage current were evaluated by changing the gate voltage at a voltage of minus 60 volts.

Examples are shown below, but the polymer synthesis reaction, purification, and drying were all performed under yellow light or under light shielding. In the examples, the reason why the reaction was carried out under yellow light or under light shielding was to prevent the photocrosslinking reaction of the photopolymerizable compound and the photocrosslinking reaction of the polymer into which the photopolymerizable compound was introduced. .

Example 1 Synthesis of 7-methacryloyloxy-4-oxo-benzopyran (7MOB) A stirrer was placed in a 100 mL two-necked flask equipped with a nitrogen inlet tube, 5 g of 7-hydroxy-4-oxo-benzopyran, dehydrated pyridine 4.9 g and 4-dimethylaminopyridine 0.8 g were charged. Next, 50 mL of dehydrated THF was charged and stirred at room temperature to obtain a uniform solution. After cooling the resulting solution with ice, 6.0 mL of methacryloyl chloride was slowly added using a syringe. After the addition, the reaction was allowed to proceed for 1 hour under ice cooling and 2 hours at room temperature. After the reaction, the solvent, pyridine, and methacryloyl chloride were distilled off under reduced pressure, and 50 mL of methylene chloride and 50 mL of water were added. This liquid was transferred to a separatory funnel and the methylene chloride layer was separated. This methylene chloride layer was washed 3 times with 100 mL of water to which 5 mL of concentrated hydrochloric acid was added, and further washed 3 times with 100 mL of a saturated aqueous sodium hydrogen carbonate solution. Further, it was washed with 100 mL of saturated saline three times. The washed methylene chloride layer was concentrated and dried to obtain 4.9 g of a solid. The obtained solid was recrystallized from ethanol to obtain 3.8 g of the intended 7-methacryloyloxy-4-oxo-benzopyran (7MOB). The obtained ¹ MO-NMR chart of 7MOB is shown in FIG. 2, and the ¹³ C-NMR chart is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.23 (d, —O—CH═CH—, 1H), δ 7.86 (d, aromatic, 1H), δ 7.31 (d, aromatic, 1H ), Δ 7.19 (dd, aromatic, 1H), δ 6.39 (d, —O—CH═CH, 1H), δ 6.33 (s, t, CH ₂ = C <, 1H), δ 5.98. (T, CH ₂ = C <, 1H), δ2.07 (s, —CH ₃ , 1H)
¹³ C-NMR (400 MHz, CDCl ₃ ): δ (ppm) 176.61 (—C (O) —CH═CH—O—), 164.70 (—OC (O) —C (CH ₃ ) =) , 156.74 (aromatic), 155.33 (aromatic), 154.65 (aromatic), 135.02 (CH ₂ = CH <), 128.21 (aromatic), 126.93 (CH ₂ = C <), 122.38 (aromatic), 119.38 (aromatic), 112.86 (aromatic), 110.95 _{(aromatic), 18.08 (CH 2 = C} (CH 3) - )
Example 2 Synthesis of 7-vinyl-4-oxo-benzopyran (7VOB) <Synthesis of 7-methyl-4-oxo-benzopyran (7MeOB)>
In a 1 L beaker containing a stir bar, 25 g of 2′-hydroxy-4′-methylacetophenone (Tokyo Kasei, reagent) and 142.5 g of triethylorthoformate (Tokyo Kasei, reagent) were added and mixed uniformly. .9 g of perchloric acid (Tokyo Kasei, reagent) was added in portions and reacted for 2 hours and 20 minutes with stirring. Thereafter, 500 mL of anhydrous diethyl ether (Tokyo Kasei, reagent) was poured into the reaction solution with stirring to precipitate the reaction product. The precipitate was filtered and washed three times with diethyl ether. The obtained green solid was transferred to a 1000 mL beaker, and 500 mL of water was added and reacted at 95 ° C. for 2.5 hours. The resulting red-purple reaction solution was cooled and allowed to stand overnight at room temperature. After adding 200 mL of dichloromethane to the reaction solution and stirring sufficiently, it was transferred to a separatory funnel and the dichloromethane layer was separated. Dichloromethane was added to the aqueous layer, and the extraction operation was performed twice. After adding to the dichloromethane layer described above, the mixture was concentrated and dried by an evaporator to obtain a dark red-brown solid. This solid was recrystallized and purified twice using hexane to obtain 13 g of 7MeOB.

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.08 (d, 1H, —CH═CH—), δ 7.81 (d, 1H, aromatic), δ 7.24 (s, 1H, aromatic), δ7 .21 (d, 1H, aromatic), δ 6.30 (d, 1H, —CH═CH—), δ 2.48 (s, 3H, —CH ₃ ).

<Synthesis of 7-bromomethyl-4-oxo-benzopyran (7BMOB)>
In a nitrogen box, a 500 mL Schlenk tube was charged with 11.8 g of 7MeOB, 22.8 g of N-bromosuccinimide, 0.15 g of azobisisobutylnitrile (AIBN), and 350 mL of dehydrated carbon tetrachloride. The mixture was stirred under a stream of nitrogen to dissolve the contents, heated, and reacted for 4 hours under reflux. After the reaction, the reaction mixture was cooled with ice and filtered. The filtrate was concentrated, and the residual solvent was removed with a vacuum pump to dryness. The obtained solid was recrystallized from hexane to obtain 4.3 g of 7BMOB.

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.18 (d, 1H, —CH═CH—), δ 7.49 (d, 1H, aromatic), δ 7.86 (d, 1H, aromatic), δ7 .42 (d, 1H, aromatic), δ 6.34 (d, 1H, —CH═CH—), δ 4.54 (s, 2H, —CH ₃ Br).

<Synthesis of 7-formyl-4-oxo-benzopyran (7FOB)>
A 300 mL reactor was charged with 29 g of sodium hydrogen carbonate and 230 mL of dimethyl sulfoxide and heated to 100 ° C. with stirring. To this, 4.5 g of 7BMOB was added in portions, and after the addition, after reacting for 1 hour, the reaction solution was poured into a beaker containing 1 kg of ice to precipitate the product. Methylene chloride was added to this slurry, and the organic layer was separated with a separatory funnel. The organic layer was washed with saturated brine, and then concentrated to dryness with an evaporator. The obtained solid was separated by silica gel column chromatography to obtain 1.7 g of 7FOB.

¹ H-NMR (CDCl ₃ , 400 MHz) δ 10.15 (s, 1 H, —CHO), δ 8.38 (d, 1 H, —CH═CH—), δ 7.98 (d, 1 H, aromatic), δ 7 .95 (d, 1 H, aromatic), δ 7.95 (d, 1 H, aromatic), δ 7.91 (dd, 1 H, aromatic), δ 6.43 (d, 1 H, —CH═CH—).

<Synthesis of 7-vinyl-4-oxo-benzopyran (7VOB)>
A 50 ML Schlenk tube was charged with 0.92 g of methyltriphenylphosphinium bromide and 10 g of THF, and then a solution of 0.29 g of potassium tert-butoxide in 14 g of THF was charged. After reacting for 4 hours at room temperature under stirring with nitrogen sealed, a slurry in which 0.3 g of 7FOB was partially dissolved in 10 g of THF was slowly added over 5 minutes. After completion of the addition, the mixture was reacted at room temperature for 19 hours. The reaction solution was poured into a dilute hydrochloric acid aqueous solution, and further 100 mL of chloroform was added and stirred sufficiently, and then transferred to a separatory funnel to separate the chloroform layer. The remaining aqueous layer was extracted three times with chloroform, and all the chloroform solutions were combined and concentrated by an evaporator to obtain a reddish brown oil. The oily product was separated by silica gel column chromatography using ethyl acetate as a mobile phase to obtain 0.06 g of 7-vinyl-4-oxo-benzopyran (7VOB) as yellow crystals. FIG. 4 shows a ¹ H-NMR chart of the obtained 7VOB.

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.16 (d, 1H, —CH═CH—), δ 7.84 (d, 1H, aromatic), δ 7.48 (d, 1H, aromatic), δ7 .42 (s, 1H, aromatic), δ 6.79 (q, 1H, —CH =), δ 6.33 (d, 1H, —CH═CH—), δ 5.95 (d, 1H, ═CH ₂ ), Δ 5.49 (d, 1H, ═CH ₂ ).

Example 3 Synthesis of bis (7- (4-oxo-benzopyranyl)) fumarate (BOBF) Under nitrogen, 5.0 g of 7-hydroxy-4-oxo-benzopyran, 4-dimethylaminopyridine was added to a 100 mL Schlenk tube. 0.15 g and N-methylpyrrolidone 50 g were charged, and the solid matter was dissolved under stirring, followed by ice cooling. Next, 1.9 g of fumaryl chloride was slowly added dropwise, and after completion of the addition, the reaction was allowed to proceed for 30 minutes under ice cooling. After further reaction at room temperature for 1.5 hours, the reaction product was poured into 300 mL of water, and the precipitate was filtered to obtain a black brown solid. The solid was added into ethanol, washed with stirring for 30 minutes, and filtered. The obtained brown solid was recrystallized using a mixed solvent of ethanol and N-methylpyrrolidone to obtain 0.8 g of bis (7- (4-oxo-benzopyranyl)) fumarate as light brown needle-like crystals. A ¹ H-NMR chart of the obtained BOBF is shown in FIG.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 8.31 (d, —O—CH═CH—C (O) —, 2H), δ 8.11 (d, aromatic, 2H), δ 7.68 (D, aromatic, 2H), δ 7.41 (dd, aromatic, 2H), δ 7.25 (s, —C (O) —CH═CH—C (O) —, 2H), δ 6.37 ( d, —O—CH═CH—C (O) —, 1H).

Example 4 Synthesis of 6- (chromone-7-oxy) hexamethyl methacrylate (6CHMA) 7- (6-hydroxyhexanoyl) -4H-chromon-1-one (HHC) is a journal of medical chemistry. It was synthesized by the method described in Journal, 2014, Vol. 57, No. 22, page 9343. A 100 mL flask was charged with 3.0 g of HHC, 1.4 g of pyridine, 0.14 g of 4-dimethylaminopyridine, and 24 g of dehydrated tetrahydrofuran (THF), and stirred at room temperature to obtain a uniform solution. After this solution was cooled by ice cooling, 1.8 g of methacryloyl chloride was slowly added. Thereafter, the reaction was carried out for 3 hours with stirring, and after adding a small amount of dibutylhydroxytoluene (BHT), all volatile components such as solvent were distilled off at 50 ° C. under reduced pressure. To the obtained solid, 50 mL of methylene chloride and 200 mL of water were added to dissolve the solid. Next, the obtained solution was transferred to a separatory funnel, 5 mL of 35% hydrochloric acid was added to wash the methylene chloride layer (oil layer), and then the oil layer was separated. This oil layer was washed three times with a saturated calcium carbonate aqueous solution and twice with a saturated saline solution, and filtered with a phase separation filter paper to separate only the oil layer. A small amount of BHT was added to the oil layer, and the mixture was concentrated by an evaporator, and volatile matter was removed from the reddish orange liquid by a vacuum pump to obtain 3.0 g of 6CHMA (orange crystals). The ¹ H-NMR of the obtained 6CHMA is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.10 (d, —CH═CH—, 1H), δ 7.78 (d, aromatic, 1H), δ 6.96 (dd, aromatic, 1H), δ 6.82 (s, aromatic, 1H), δ 6.28 (d, —CH═CH—, 1H), δ 6.10 (s,> C═CH ₂ —, 1H), δ 5.56 (s,> C = CH ₂ —, 1H), δ 4.17 (t, —CH ₂ OC (O) —, 2H), δ 4.04 (t, —OCH ₂ —, 2H), δ 1.95 (s, —CH ₃ , 3H), δ 1.87 to 1.47 (m, — (CH ₂ ) ₄ —, 8H)
(Example 5)
1.05 g of isobutyl methacrylate, 0.45 g of 7MOB, 7.5 g of DMF, and 93 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 65 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 1.0 g of powdery polymer 1. The resulting polymer 1 contained 29 mol% of 7-methacryloyloxy-4-oxo-benzopyran units. ¹ H-NMR of the obtained polymer 1
A chart is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.21 (br, —C (O) —CH═CH—O—), δ 7.87 (br, aromatic), δ 7.38 to 7.13 (m , Aromatic), δ6.34 (br, —C (O) —CH═CH—O—), δ2.07 to 1.83 (m,> C (CH ₃ ) —,> CH—), δ1. 22 to 0.96 (m, —CH ₂ —, —CH ₃ )

<Production and evaluation of organic transistor element>
Labo Coater (Nippon Parylene Co., Ltd., commercial product) 0.2 g of dichlorodiparaxylylene (Nippon Parylene Co., Ltd., trade name DPX-C) on 30 x 30 mm ² glass (base material) (Corning Eagle XG) No. PDS2010) was vacuum-deposited to form a planarization layer of poly (parachloroxylylene). Further, a silver electrode was vacuum-deposited on the planarizing layer using a mask to form an electrode having a thickness of 30 nm. Then, it was immediately immersed in a 2-propanol solution of pentafluorobenzenethiol 30 mmol / L, taken out after 5 minutes, washed with 2-propanol, and blow-dried. On the substrate on which the electrode is formed, a 0.2 wt% toluene solution of 2,7-di (n-hexyl) dithienobenzodithiophene is drop-cast, and naturally dried at room temperature (25 ° C.) to form an organic semiconductor layer. Formed. Further, a 2-butanol solution (5 wt%) of polymer 1 was spin-coated on the organic semiconductor layer under conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds, and dried at 100 ° C. for 10 minutes. A contact hole mask was used for this element, a UV light intensity of 4 kW / cm ² was used, UV irradiation was performed at room temperature for 5.4 seconds, and photocrosslinking was performed at a UV irradiation amount of 300 mJ / cm ² . A gate insulating layer was formed. Further, a silver electrode having a thickness of 30 nm was vacuum deposited on the gate insulating layer using a mask. Next, this element was immersed in toluene for 1 minute to form a contact hole, and a top gate / bottom contact (TGBC) type organic transistor element was produced. Table 1 shows the evaluation results and the like of the manufactured organic transistor.

Polymer 1 was photocrosslinked with a low UV dose, and it was confirmed that an insulating layer having excellent solvent resistance was formed, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.

(Example 6)
0.78 g of isobutyl methacrylate, 0.23 g of 7MOB, 5.0 g of DMF, and 109 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.55 g of Polymer 2. The resulting polymer 2 contained 19 mol% 7-methacryloyloxy-4-oxo-benzopyran units.

<Production and evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 2. An evaluation result etc. are shown according to Table 1.

Polymer 2 was photocrosslinked at a low UV irradiation amount, and it was confirmed that an insulating layer having excellent solvent resistance was formed, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.

(Example 7)
0.86 g of isobutyl methacrylate, 0.15 g of 7MOB, 5.0 g of DMF, and 108 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.67 g of Polymer 3. The resulting polymer 3 contained 12 mol% 7-methacryloyloxy-4-oxo-benzopyran units.

<Production and evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 3. An evaluation result etc. are shown according to Table 1.

It was confirmed that the polymer 3 was photocrosslinked with a low UV irradiation amount to form an insulating layer with excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.

(Example 8)
0.86 g of isobutyl methacrylate, 0.15 g of 7MOB, 5.0 g of DMF, and 108 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.68 g of Polymer 4. The resulting polymer 4 contained 16 mol% 7-methacryloyloxy-4-oxo-benzopyran units.

<Production and evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 4. An evaluation result etc. are shown according to Table 1.

It was confirmed that the polymer 4 was photocrosslinked with a low UV irradiation amount to form an insulating layer having excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.

Example 9
0.77 g of isobutyl methacrylate, 0.23 g of 7VOB, 5 g of DMF, and 11 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 65 ° C. for 6 hours under a nitrogen seal. The obtained polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.6 g of polymer 5. The resulting polymer 5 contained 26 mol% 7-vinyl-4-oxo-benzopyran units.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.9 (brs, —C (O) —CH═CH—O—), δ 7.79 (brs, aromatic), δ 7.07 to 6.94 (brm) , Aromatic), δ 6.28 (br, —C (O) —CH═CH—O—), δ 3.67 (brs, —OCH ₂ —), δ 1.89 to 1.80 (brm, —CH < ), Δ1.00 to 0.67 (brm,> C (CH ₃ ) —, —CH ₂ —, —CH ₃ )

<Production and evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 5. An evaluation result etc. are shown according to Table 1.

It was confirmed that the polymer 5 was photocrosslinked at a low UV irradiation amount to form an insulating layer having excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.

(Comparative Example 1)
A top gate / bottom contact (TGBC) type organic transistor was prepared in the same manner as in Example 5 except that the polymer 1 was changed to poly (n-butyl methacrylate) (PNBMA). PNBMA was not photocrosslinked by ultraviolet rays, and it was confirmed that the flatness of the film surface was lost due to heat when vacuum-depositing the source electrode and the drain electrode. Moreover, there was no solvent resistance, and the PNBMA film was dissolved at the time of contact hole formation, so that an organic transistor element could not be produced. Table 1 shows the evaluation results.

(Comparative Example 2)
A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5 except that the polymer 1 was changed to poly (n-octyl methacrylate) (PNOMA). It was confirmed that PNOMA was not photocrosslinked by ultraviolet rays, and the flatness of the film surface was lost due to the heat when vacuum-depositing the source electrode and the drain electrode. Further, the organic transistor element was not able to be produced because it had no solvent resistance and the PNOMA film was dissolved when the contact hole was formed. Table 1 shows the evaluation results.

(Comparative Example 3)
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to polyvinyl butyral (PVB). The PVB resin was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. Further, the PVB film was not dissolved in toluene, and when butanol was used, the PVB film was dissolved and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.

(Comparative Example 4)
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to polyvinyl alcohol (PVA). PVA was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. Further, the PVA film was not dissolved in toluene, and when butanol was used, the PVA film was dissolved and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.

(Comparative Example 5)
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to a fluorine-based cyclic ether polymer (Cytop). Cytop was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. The Cytop film was not dissolved in toluene, and when the fluorinated solvent CYTOP CT-SOLV180 was used, the Cytop film was dissolved and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.

(Comparative Example 6)
The solubility and solvent resistance were evaluated in the same manner as in Example 5 except that the polymer 1 was used and ultraviolet rays were not irradiated. Polymer 1 was dissolved in n-butanol, and the residual film ratio was 0.
<Production and evaluation of organic transistor element>
A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5. The polymer 1 did not have solvent resistance, the entire film was dissolved, and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.

(Example 10)
2 g of styrene, 0.78 g of 7MOB, 14 g of DMF, and 39 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 65 ° C. for 6 hours under a nitrogen seal. The obtained polymer solution was poured into 300 mL of methanol under stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.4 g of polymer 6. The resulting polymer 6 contained 28 mol% 4-oxo-benzopyran units (formula (4)) and 72 mol% styrene monomer units (formula (7)). A ¹ H-NMR chart of the obtained polymer 6 is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.98 (brd, —C (O) —CH═CH—O—, δ 7.80 (br, aromatic), δ 7.03 to 6.08 (brm, Aromatic), δ 6.46 (brs, —C (O) —CH═CH—O—), δ 2.63 to 0.24 (brm, —CH <, —CH ₂ —).

<Production and evaluation of organic transistor 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 (5 wt%) of the obtained polymer 6 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 100 ° C. for 10 minutes ( Insulating film formation) Using a light source with an ultraviolet intensity of 4 kW / cm ² , UV irradiation is performed at room temperature for 5.4 seconds, and crosslinking is performed under the condition of an ultraviolet irradiation amount of 300 mJ / cm ^2. Formed. 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 an electrode width of 500 μm. Thereafter, it was immediately immersed in an isopropanol solution of 30 mmol of pentafluorobenzenethiol, 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 evaporated and dried at 50 ° C. for 1 hour, a bottom gate / bottom contact (BGBC) type organic transistor device was produced. Table 2 shows the configuration, evaluation results, and the like of the fabricated organic field effect transistor device.

(Example 11)
A 25 mL Schlenk tube was charged with 0.3 g of BOBF obtained in Example 3, 0.012 g of azoisobutyronitrile (AIBN), 0.7 g of styrene, and 7.5 g of N-methylpyrrolidone, and freeze degassing with liquid nitrogen. And dissolution was repeated 4 times, followed by polymerization at 73 ° C. for 6 hours under nitrogen pressure. After completion of the polymerization, the reaction solution was poured into 100 mL of methanol to precipitate a polymer, filtered and washed with methanol, and then dried at 50 ° C. to obtain 0.5 g of light brown polymer 7. The resulting polymer 7 had 4 mol% of BOBF-derived repeating units (formula (5)) and 96 mol% of styrene units (formula (7)). A ¹ H-NMR chart of the obtained polymer 7 is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.12 (brs, —O—CH═CH—C (O) —), δ 8.05 (brs, —O—CH═CH—C (O) —) , Δ 7.79 (brs, aromatic), δ 6.33 (brs, —O—CH═CH—C (O) —, H), δ 3.14, δ 2, 72, δ 2.29, δ 2.24, δ 1 .83, δ1.60, δ1.42 (brm, —CH <, —CH ₂ —)

<Production and evaluation of organic transistor element>
Table 2 shows the results and the like of an organic transistor element prepared and evaluated in the same manner as in Example 10 except that the polymer 6 was changed to the polymer 7.

Example 12
7MOB 0.35g, THF 14g, and AIBN 17.5mg were charged into a 20ML Schlenk tube and sufficiently deaerated, and then PFS 1.65g was charged in a nitrogen box. After sufficiently performing nitrogen substitution again, polymerization was performed at 60 ° C. for 6 hours under a nitrogen seal. The obtained polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.4 g of polymer 8. The resulting polymer 8 comprises 16 mol% 4-oxo-benzopyran units (formula (4)) and 84

mol%

2,3,4,5,6-pentafluorostyrene styrene (PFS) monomer units ( (7)). A ¹ H-NMR chart of the obtained polymer 8 is shown in FIG.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.17 (brd, —C (O) —CH═CH—O—, δ 7.86 (brs, aromatic), δ 6.92 (brs, aromatic), δ6.35 (brs, —C (O) —CH═CH—O—), δ3.00 to 0.91 (brm, —CH <, —CH ₂ —).

<Production and evaluation of organic transistor element>
Table 2 shows the results obtained by producing an organic transistor element in the same manner as in Example 10 except that the polymer 6 is changed to the polymer 8.

(Example 13)
1.0 g of styrene, 0.78 g of 7MOB, 18 g of THF, and 39 mg of AIBN were charged into a 20 ML Schlenk tube and sufficiently deaerated, and then 1.86 g of PFS was charged in a nitrogen box. After sufficiently performing nitrogen substitution again, polymerization was performed at 60 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring and precipitated, and the precipitate was filtered and dried under reduced pressure to obtain 0.5 g of polymer 9. The obtained polymer 9 was composed of 21 mol% of 4-oxo-benzopyran unit (formula (4)), 42 mol% of 2,3,4,5,6-pentafluorostyrene monomer unit (formula (7) ) And 37 mol% of styrene monomer units (formula (7)) (formula (7) is 79 mol% in total).

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.0 (brd, —C (O) —CH═CH—O—, δ 7.86 to 6.08 (brm, aromatic), δ 6.41 (brs, —C (O) —CH═CH—O—), δ3.00 to 0.24 (brm, —CH <, —CH ₂ —).

<Production and evaluation of organic transistor element>
Table 2 shows the results obtained by producing and evaluating an organic transistor element in the same manner as in Example 10 except that the polymer 6 is changed to the polymer 9.

(Example 14)
A 20-ML Schlenk tube was charged with 0.232 g of 7VOB, 0.708 g of styrene, 14 mg of AIBN, and 5 g of dimethylformamide. After nitrogen substitution, polymerization was performed at 60 ° C. for 6 hours under nitrogen pressure. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The obtained polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and reprecipitated. Then, the precipitate was filtered and dried under reduced pressure to obtain 0.6 g of the polymer 10. The resulting polymer 10 contained 35 mol% 4-oxo-benzopyran units (formula (43)) and 37 mol% styrene monomer units (formula (7)).

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.76 (brs, —C (O) —CH═CH—O—, δ 6.99 (brs, aromatic), δ 6.34 (brs, aromatic), δ 6.29 (brs, aromatic, —C (O) —CH═CH—O—), δ 2.67 to 1.41 (brm, —CH <, —CH ₂ —).

<Production and evaluation of organic transistor element>
Table 2 shows the results of producing and evaluating an organic transistor element in the same manner as in Example 10 except that the polymer 6 was changed to the polymer 10.

(Comparative Example 7)
Solubility, UV crosslinkability, and solvent resistance were evaluated in the same manner as in Example 10 except that the polymer 6 was changed to an FCE polymer (Cytop, manufactured by AGC Asahi Glass Co., Ltd.). The FCE polymer did not dissolve in any of the test solvents and could not be formed using a general-purpose solvent. Moreover, it was dissolved in the fluorine-based solvent PFTBA and irradiated with UV, but it was not crosslinked, and the remaining film ratio with respect to this solvent was 0. Accordingly, UV irradiation to the FCE polymer layer was omitted, and an organic transistor device was produced in the same manner as in Example 10. On the substrate on which the gate electrode, FCE polymer layer, source and drain were formed, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was printed with a dispenser. A uniform organic semiconductor crystal film was not formed, and the organic transistor device did not operate. An evaluation result etc. are shown according to Table 2.

(Comparative Example 8)
Solubility, UV crosslinkability, and solvent resistance were evaluated in the same manner as in Example 10 except that the polymer 6 was changed to polystyrene (PS) (Aldrich reagent). PS was not crosslinked by UV irradiation, and the remaining film ratio with respect to the test solvent was zero.

<Production and evaluation of organic transistor element>
In the same manner as in Example 10, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was dispensed on the substrate on which the gate electrode, FCE polymer layer, source and drain were formed. However, the PS film was dissolved by this solution, an organic semiconductor film having good properties was not formed, and the device did not operate as an organic transistor device. An evaluation result etc. are shown according to Table 2.

(Comparative Example 9)
Solubility, UV crosslinkability, solvent resistance were the same as in Example 10 except that the polymer 6 was changed to poly (2,3,4,5,6-pentafluorostyrene) (PPFS) (Aldrich reagent). Sex was evaluated. PPFS was not crosslinked by UV irradiation, and the residual film ratio with respect to the test solvent was 0.

<Production and evaluation of organic transistor element>
In the same manner as in Example 10, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was dispensed on the substrate on which the gate electrode, FCE polymer layer, source and drain were formed. However, the PPFS film was dissolved by this solution, an organic semiconductor film having good properties was not formed, and the device did not operate as an organic transistor device. An evaluation result etc. are shown according to Table 2.

(Comparative Example 10)
<Resin synthesis>
In a nitrogen box, a 300 mL Schlenk tube was charged with 5.0 g of polystyrene (Aldrich reagent), 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 a 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, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, and then dried under reduced pressure at 50 ° C. to obtain 5.9 g of the polymer 11. Obtained. As a result of analysis by ¹ H-NMR, the obtained polymer 11 has 85 mol% of styrene monomer units (formula (7)) and 15 mol% of photocrosslinking group (chalcone group) units. It was 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 —).

<Production and evaluation of organic transistor element>
The polymer 11 was dissolved in the test solvent, but contained a gel and could not be filtered with a 0.22 μm filter. Therefore, after the polymer toluene solution having a concentration of 1 wt% is filtered through a 10 μm, 5 μm, 3 μm, 1 μm, 0.5 μm, and 0.22 μm filter in order, the polymer solution is concentrated by an evaporator to reduce the polymer concentration. Table 2 shows the results of producing and evaluating an organic transistor element in the same manner as in Example 10 except that the polymer 6 was changed to the polymer 11 after setting it to 5 wt%. Polymer 11 was inferior in filterability and UV crosslinkability as compared with the polymers of Examples 10-14.

(Comparative Example 11)
The polymer 6 obtained in Example 10 was used, and the solubility and solvent resistance were evaluated by the same method as in Example 10 except that ultraviolet rays were not irradiated. The polymer 6 was dissolved in the test solvent and the remaining film rate was 0.

<Production and evaluation of organic transistor element>
In the same manner as in Example 10, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was dispensed on a substrate on which a gate electrode, a polymer layer, a source and a drain were formed using a dispenser. Although it was printed, the polymer film was dissolved by this solution, an organic semiconductor film having good properties was not formed, and it did not operate as an organic transistor device. An evaluation result etc. are shown according to Table 2.

(Example 15)
In a nitrogen box, put a magnetic stir bar in a 20 ML Schlenk tube, 7.1 mg of azobisisobutyronitrile (AIBN), monomer with inhibitor removed (0.27 g of 6CHMA, and 1H, 1H, 2H, 2H -Heptadecafluorodecyl methacrylate (HFDMA) (1.73 g), toluene (4.3 g), α, α, α, α ', α', α'-hexafluoro-m-xylene (HFMX) (7 g), Gas (freezing with liquid nitrogen, degassing, thawing by heating) was performed 4 times. Under stirring, the mixture was heated under nitrogen pressure and polymerized at 60 ° C. for 6 hours. Then, an appropriate amount of a polymerization inhibitor (BHT) solution was added to the Schlenk tube and stirred for 1 minute, and then cooled to room temperature. The obtained reaction solution was poured into a 500 mL methanol solution to precipitate a polymer, and vacuum dried at 50 ° C. to obtain 0.7 g of the polymer 12. The resulting polymer 12 contained 79 mol% HFDMA units and 21 mol% 6CHMA units. FIG. 11 shows a ¹ H-NMR chart of the polymer 12 measured by dissolving it in a mixed solvent of deuterated chloroform and HFMX.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.02 (s, —CH═CH—), δ 7.89 (s, aromatic), δ 6.84 (brs, aromatic), δ 6.67 (brs, Aromatic), δ 6.09 (brs, —CH═CH—), δ 4.30 (brs, —OCH ₂ —), δ 3.97 (brs, —OCH ₂ —), δ 2.48 (brs, —CH _2). CF ₂ −), δ 2.14 to 1.12 (brm, —CH ₂ —), δ 1.55 (s, —CH ₃ )
The polymer 12 was dissolved in the solvent I, spin-coated on a glass plate, and the solvent resistance, contact angle, and surface tension of the UV-crosslinked polymer film were measured. The polymer 12 was dissolved in the solvent I to form a polymer film having excellent solvent resistance at room temperature and a UV irradiation amount of 100 mJ / cm ² . Moreover, the outstanding liquid repellency with respect to water and tetralin was shown. In addition, the solvent I to III had a small contact angle and excellent wettability, but did not dissolve and had excellent solvent resistance.

<Creation and evaluation of organic transistor element>
Parylene-C (manufactured by Japan Parylene Godo Kaisha) and SCS Lab Coater 2 (manufactured by Japan Parylene Godo Kaisha (model PDS2010)) are used on 30 × 30 mm ² glass (base material) (Eagle XG manufactured by Corning). Then, a film was formed by a vacuum evaporation method to form an insulating layer 1 having a thickness of 300 nm (substrate 1). Gold was vacuum-deposited on this substrate (1) to form a source electrode and a drain electrode having a thickness of 50 nm, a channel length of 50 μm, and an electrode width of 50 μm. Then, it was immersed in an isopropanol solution of 30 mmol of pentafluorobenzenethiol for 5 minutes, washed with isopropanol, and blow-dried (substrate 2).

Next, a HFMX solution (2 wt%) of the polymer 12 was spin-coated on the substrate 2 under conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds to form a polymer film having a thickness of 100 nm. The polymer film was crosslinked by irradiating with 100 mJ / cm ² ultraviolet rays through a partition wall forming mask, and washed with HFMX to remove uncrosslinked portions (substrate 3).

Thereafter, 60 nL of a 0.8 wt% toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) was printed on the substrate 3 with a dispenser, and baked at 50 ° C. for 1 hour (substrate 4). Further, an HFMX solution (5 wt%) of the polymer 12 was spin coated on the upper surface of the substrate 4 under conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds to form an insulating layer having a thickness of 300 nm (substrate 5). Aluminum was vacuum-deposited on this to form a gate electrode having a thickness of 50 nm, and an organic transistor element was obtained.

The shape of the partition after the same polymer 12 was laminated on the partition formed using the polymer 12 and the thickness thereof were not changed, and the laminate was excellent. The dielectric breakdown strength was also high, and it was confirmed that the transistor operates stably as an organic transistor. The evaluation results are shown in Table 4.

(Example 16) In a nitrogen box, a magnetic stirrer was placed in a 20-ML Schlenk tube, 6.6 mg of AIBN, and the monomer from which the inhibitor was removed (6CHMA 0.24 g, and 1H, 1H, 2H, 2H-heptadecafluoro Decyl methacrylate (HFDMA) 1.76 g), toluene 3.0 g, α, α, α, α ′, α ′, α′-hexafluoro-m-xylene (HFMX) 4.9 g, and then deaerated ( Freezing with liquid nitrogen, deaeration, and thawing by heating) were performed 4 times. Under stirring, heated in a pressurized state with nitrogen, polymerized at 60 ° C. for 6 hours, added a suitable amount of a polymerization inhibitor dibutylhydroxytoluene (BHT) in a Schlenk tube, stirred for 1 minute, and then cooled to room temperature. did. The obtained reaction solution was poured into a 500 mL methanol solution to precipitate a polymer, filtered and washed with methanol, and then vacuum dried at 50 ° C. to obtain 0.7 g of the polymer 13. The resulting polymer 13 contained 82 mol% HFDMA units and 18 mol% 6CHMA units.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.02 (s, —CH═CH—), δ 7.89 (s, aromatic), δ 6.84 (brs, aromatic), δ 6.67 (brs, Aromatic), δ 6.09 (brs, —CH═CH—), δ 4.30 (brs, —OCH ₂ —), δ 3.97 (brs, —OCH ₂ —), δ 2.48 (brs, —CH _2). CF ₂ −), δ 2.14 to 1.12 (brm, —CH ₂ —), δ 1.55 (s, —CH ₃ )
The solvent resistance, contact angle, and surface tension of the polymer film were measured in the same manner as in Example 15 except that the polymer 12 was changed to the polymer 13. The evaluation results are shown in Table 3. It was confirmed that the polymer 13 was excellent in solubility in a solvent, UV crosslinkability at room temperature, liquid repellency, and laminating property of a fluororesin on a partition wall. Moreover, it operated stably as an organic transistor. The evaluation results are shown in Table 4.

(Example 17)
In a nitrogen box, put a magnetic stir bar in a 20 ML Schlenk tube, AIBN 6.8 mg, monomer with inhibitor removed (6CHMA 0.34 g, and 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (HFDMA) 1.66 g), 3.0 g of toluene, 4.9 g of α, α, α, α ′, α ′, α′-hexafluoro-m-xylene (HFMX), and then degassed (freeze with liquid nitrogen, Degassing and melting by heating) were performed 4 times. Under stirring, the mixture was heated under nitrogen pressure and polymerized at 60 ° C. for 6 hours. Then, an appropriate amount of a polymerization inhibitor (BHT) solution was added to the Schlenk tube and stirred for 1 minute, and then cooled to room temperature. The obtained reaction solution was poured into a 500 mL methanol solution to precipitate a polymer, and vacuum dried at 50 ° C. to obtain 0.9 g of the polymer 14. The resulting polymer 14 contained 75 mol% HFDMA units and 25 mol% 6CHMA units.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.02 (s, —CH═CH—), δ 7.89 (s, aromatic), δ 6.84 (brs, aromatic), δ 6.67 (brs, Aromatic), δ 6.09 (brs, —CH═CH—), δ 4.30 (brs, —OCH ₂ —), δ 3.97 (brs, —OCH ₂ —), δ 2.48 (brs, —CH _2). CF ₂ −), δ 2.14 to 1.12 (brm, —CH ₂ —), δ 1.55 (s, —CH ₃ )
The solvent resistance, contact angle, and surface tension of the polymer film were measured in the same manner as in Example 15 except that the polymer 12 was changed to the polymer 14. The evaluation results are shown in Table 3. It was confirmed that the polymer 14 was excellent in solubility in a solvent, UV crosslinkability at room temperature, liquid repellency, and laminating property of a fluororesin on a partition wall. Moreover, it operated stably as an organic transistor. The evaluation results are shown in Table 4.

(Comparative Example 12)
In a nitrogen box, put a magnetic stir bar in a 20 ML Schlenk tube, AIBN 6.2 mg, 2.0 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (HFDMA) with the inhibitor removed, 3.0 g of toluene , Α, α, α, α ′, α ′, α′-hexafluoro-m-xylene (HFMX) 4.9 g, and then degassing (freezing with liquid nitrogen, degassing, melting by heating) 4 times. Under stirring, the mixture was heated under nitrogen pressure and polymerized at 60 ° C. for 6 hours. Then, an appropriate amount of a polymerization inhibitor (BHT) solution was added to the Schlenk tube and stirred for 1 minute, and then cooled to room temperature. The obtained reaction solution was poured into a 500 mL methanol solution to precipitate a polymer, and vacuum dried at 50 ° C. to obtain 0.5 g of the polymer 15.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.97 (brs, —OCH ₂ —), δ 2.48 (brs, —CH ₂ CF ₂ —), δ 2.14 to 1.12 (brm, —CH ₂ -), Δ1.55 (s, -CH ₃ )
The solvent resistance, contact angle, and surface tension of the polymer film were measured in the same manner as in Example 15 except that the polymer 12 was changed to the polymer 15. The evaluation results are shown in Table 3. Polymer 15 is excellent in solvent solubility and liquid repellency, but does not undergo UV crosslinking at room temperature and does not have solvent resistance, so that the partition walls are dissolved by stacking the fluororesin on the partition walls. It was confirmed that it was difficult. Organic transistors have low mobility, and the mobility between elements varies. The evaluation results are shown in Table 4.

(Comparative Example 13)
The polymer 12 was changed to Cytop (manufactured by AGC Asahi Glass Co., Ltd.), and the solvent resistance, contact angle, and surface tension of the polymer film were changed in the same manner as in Example 15 except that the solvent I was changed to the solvent II. It was measured. The evaluation results are shown in Table 3. CYTOP has excellent solubility in solvents and liquid repellency, but it does not undergo UV crosslinking at room temperature and has no solvent resistance. Therefore, lamination of fluorocarbon resin on the partition walls dissolves the partition walls. It was confirmed that it was difficult.

(Comparative Example 14)
The solvent resistance of the polymer film was changed in the same manner as in Example 15 except that the polymer 12 was changed to Teflon (registered trademark) -AF (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) and the solvent I was changed to the solvent III. , Contact angle, and surface tension were measured. The evaluation results are shown in Table 3. Teflon (registered trademark) -AF is excellent in solvent solubility and liquid repellency, but does not undergo UV crosslinking at room temperature and does not have solvent resistance, so the partition walls dissolve by lamination of fluororesin on the partition walls. Therefore, it was confirmed that lamination was difficult. Organic transistors have low mobility, and the mobility between elements varies. The evaluation results are shown in Table 4.

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. 2018-057039 filed on March 23, 2018, Japanese Patent Application No. 2019-048884 filed on March 12, 2019, Japanese Patent Application filed on May 11, 2018 Application No. 2018-092191, Japanese Patent Application No. 2019-044889 filed on Mar. 12, 2019, Japanese Patent Application No. 2018-128598 filed on Jul. 5, 2018, Specification, Sequence Listing, Patent The entire contents of the claims, drawings and abstract are hereby incorporated by reference as the disclosure of the specification of the present invention.

Resins suitable for forming insulating layers for high-quality organic transistor devices that can be manufactured by printed electronics technology can be provided.

(A): Bottom gate-top contact type organic transistor (B): Bottom gate-bottom contact type organic transistor (C): Top gate-top contact type organic transistor (D): Top gate-bottom contact type organic transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims

A polymerizable compound represented by formula (1).

(In the formula (1), R 1 represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R 2 and R 3 is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl One kind of the group consisting of an ether group, an arylthio group, a carboxyalkyl group, a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group X represents O or S, and m represents an integer of 0 to 3.)
A polymerizable compound represented by formula (2).

(In Formula (2), Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1, G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group and each X 1 ~ X 4 are independently O or S, r and s which Independently represents an integer of 0 to 3.).
A polymer comprising at least one of the formulas (3) to (5) as a repeating unit and at least one repeating unit of the group consisting of the following formulas (6) to (8).

(In the formula (3), R 1 represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R 2 and R 3 is each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthioether group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, Aryl ether group, aryl thioether group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothioether group, cycloalkyl group, cycloheteroalkyl One of the group consisting of groups, X is O or S, m is 0 to Of an integer.)

(In the formula (4), R 1 represents either hydrogen or a C1-C6 alkyl group, L represents a divalent linking group having 1 to 14 carbon atoms, n represents 0 or 1, and A, R 2 and R 3 is each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthioether group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, Aryl ether group, aryl thioether group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothioether group, cycloalkyl group, cycloheteroalkyl One of the group consisting of groups, X is O or S, m is 0 to Of an integer.)

(In the formula (5), Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1, G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group the one of the group consisting of, X 1 ~ X 4 are each independently O or S, And s each independently represents an integer of 0-3.)

(In the formula (6), R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.)

(In the formula (7), R 9 is either hydrogen or a C1-C6 alkyl group, M is a divalent linking group having 1 to 14 carbon atoms, k is 0 or 1, Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group, and j is 0 to Represents an integer of 5.)

(In formula (8), R 10 represents hydrogen or a C1-C6 alkyl group, E represents —O—, —S—, or —NH—, t represents 0 or 1, and R 11 represents 1 to Represents 18 fluoroalkyl groups.)
The polymer of Claim 3 containing the repeating unit represented by Formula (4) and the following formula | equation (6).

(Here, R 1 , L, n, A, R 2 , R 3 , X and m are the same as those defined in the formula (1).)

(Here, R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.)
The polymer of Claim 3 which contains at least any one of Formula (4) or Formula (5) as a repeating unit, and contains the repeating unit represented by the following formula | equation (7).

(Here, R 1 , L, n, A, R 2 , R 3 , X and m are the same as those defined in the formula (1).)

(Here, Q 1 , Q 2 , p, q, G 1 , G 2 , R 4 to R 7 , X 1 to X 4 , r and s are the same as those defined in the formula (2)). .)

(In the formula (7), R 9 is either hydrogen or a C1-C6 alkyl group, M is a divalent linking group having 1 to 14 carbon atoms, k is 0 or 1, Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group, and j is 0 to Represents an integer of 5.)
The polymer of Claim 3 containing the repeating unit represented by Formula (4) and the following formula | equation (8).

(Here, R 1 , L, n, A, R 2 , R 3 , X and m are the same as those defined in the formula (1).)

(Where R 10 is hydrogen or a C1-C6 alkyl group, E is —O—, —S—, or —NH—, t is 0 or 1, and R 11 is a fluoro having 1 to 18 carbon atoms. Represents an alkyl group.)
The crosslinked product of the polymer according to claim 3.
An insulating film containing at least one of the polymer according to claim 3 or the crosslinked product according to claim 7.
A protective film comprising at least one of the polymer according to claim 4 or the crosslinked product according to claim 7.
A liquid repellent film comprising at least one of the polymer according to claim 6 or the crosslinked product according to claim 7.
An organic transistor device comprising the insulating film according to claim 8.
An organic transistor device comprising the protective film according to claim 9.
An electronic device comprising the liquid repellent film according to claim 10.