JP2019112634A - Light crosslinkable polymer, insulating layer and organic transistor device containing the same - Google Patents

Abstract

To provide an insulating layer-forming resin that can be applied by solution coating onto an organic semiconductor layer contained in an organic transistor device.SOLUTION: A resin contains a repeating unit (1) composed of a (meth) acrylate composed of a C2-18 alkyl group and a repeating unit represented by formula (2). (a, b independently represent 1 or 2, c is 0 or 1. m is an integer of n-2 or greater, n is a number of carbon atoms of the longest alkyl chain in the repeating unit (1).SELECTED DRAWING: None

Description

  The present invention relates to a resin for forming an insulating layer which can be solution-coated on an organic semiconductor layer contained in an organic transistor device.

  In the production of the top gate type organic transistor device, after forming the organic semiconductor layer, it is necessary to laminate a polymer film (insulating layer) on the organic semiconductor layer. In this case, it is essential that the polymer solution in which the polymer is dissolved in the organic solvent does not affect the already formed organic semiconductor layer. Therefore, the solution should not dissolve the organic semiconductor layer. However, many organic semiconductors are often at least partially dissolved by various general-purpose organic solvents, although there is a difference in solubility.

  At present, as a method of forming an insulating layer on the upper surface of the organic semiconductor layer, for example, a method of forming a polyparaxylylene film by vapor deposition is known. In this method, a raw material is heated without using a solvent, and vapor deposition polymerization is performed on a substrate under vacuum to form a polyparaxylylene thin film. Therefore, the organic semiconductor layer can be prevented from being dissolved by contact with the solvent. On the other hand, this method limits the size of the substrate that can be processed, has problems in that continuous production by the whole printing process is difficult, and furthermore, it is not economical because of the batch process.

  As another method, there is known a method of applying a solution in which a cyclic fluorine-based ether resin is dissolved in a fluorine-based solvent on the upper surface of the organic semiconductor layer. Since many of the currently known organic semiconductors do not dissolve in the fluorine-based solvent, this method can form the insulating layer of the cyclic fluorine-based ether resin on the layer without affecting the organic semiconductor layer. On the other hand, both the fluorocarbon resin and the fluorocarbon solvent have a problem in economy, and furthermore, since the fluorocarbon resin solution has a low affinity with the organic semiconductor, the fluorocarbon resin layer and the organic semiconductor layer There is a problem that the performance of the organic field effect transistor device is lowered because the adhesion of

  Even if it coats on the upper surface of an organic-semiconductor layer, aliphatic alcohol is one of the highly versatile solvents which does not corrode a wide variety of organic-semiconductor layers. A low-boiling lower aliphatic alcohol is preferable as the solvent because a high-boiling aliphatic alcohol reduces the semiconductor performance if it remains in the insulating layer. As resins which are soluble in lower aliphatic alcohols, butyral resins, polyvinyl alcohols, alkyl methacrylates having a specific structure, and the like are known. However, butyral resin and polyvinyl alcohol have hydroxyl groups, and these hydroxyl groups trap electric charges to lower the semiconductor performance, and therefore are not suitable as a polymer forming an insulating layer. On the other hand, alkyl methacrylates such as poly (n-butyl methacrylate) and poly (n-octyl methacrylate) are dissolved in lower aliphatic alcohols (see, for example, Non-Patent Document 1) and have no hydroxyl group, so they can be used as insulating layer materials. The charge trap problem is less likely to occur when used. However, these polymers do not have crosslinkability, and when used as an insulating layer, they do not exhibit solvent resistance to organic solvents. Therefore, when the metal ink solution is applied to form an electrode on the insulating layer after the formation of the insulating layer, the solvent used for the metal ink is greatly restricted.

  From such a background, the above-mentioned resin is required to be crosslinkable, and heat or radiation is generally used as the crosslinking of the resin. Among them, when applying crosslinking (photocrosslinking) by radiation to the insulating layer formed on the upper part of the organic semiconductor layer, the organic semiconductor may be deteriorated by the radiation which has passed through the transparent insulating layer. It is preferable to make the light irradiation amount at the same time as low as possible. From this point of view, a resin for forming an insulating layer that can be photocrosslinked in a short time is required.

  As a photocrosslinkable resin having such characteristics, for example, as a polymer having an anthryl group introduced as a photocrosslinking group, a copolymer of 6- (anthracene-9-yl) hexyl methacrylate and fluoroalkyl methacrylate (eg, non-polymer) Patent Document 2), a diblock copolymer composed of poly (2-ethylhexyl methacrylate) and poly (9-anthrylmethyl methacrylate) (see, for example, Non-patent Document 3), 6- (9-anthryloxy) hexyl A technique related to methacrylate homopolymer (see, for example, Non-Patent Document 4) is disclosed. However, these documents do not mention at all the solubility of the above-mentioned polymers in lower aliphatic alcohols, and in fact, these polymers do not dissolve in lower aliphatic alcohols.

  As described above, the technology relating to the resin for forming the photocrosslinkable insulating layer which is dissolved in the lower aliphatic alcohol as described above has not been disclosed, and a resin for forming the insulating layer having both of these characteristics has been desired.

Willy Interscience, Polymer Handbook, 3rd Edition Journal of Polymer Science, 2015, 53, 1252 Journal of Polymer Science, 2016, 54, 2302 Journal of Photoscience, 2002, Vol. 9, No. 3, p. 57

  The present invention has been made in view of the above problems, and an object thereof is to provide a resin for forming an insulating layer which is soluble in a lower aliphatic alcohol and photocrosslinkable.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discover that a specific resin can melt | dissolve in a lower aliphatic alcohol and can form the photocrosslinkable insulating layer, and complete the present invention. The

  That is, the present invention relates to a resin containing the repeating unit represented by the formula (1) and the formula (2), an insulating layer using the resin, and an organic transistor using the insulating layer.

(In formula (1), R ₁ represents hydrogen or a CH ₃ group, and R ₂ represents an alkyl group having 2 to 18 carbon atoms.)

(In formula (2), R ₃ represents hydrogen or a CH ₃ group, a and b each independently represent 1 or 2, c represents 0 or 1, and m represents an integer of 2 or more. , N represents the number of carbon atoms of the longest alkyl chain in R ₂ in the formula (1).)
The present invention will be described in detail below.

  The resin of the present invention is a resin containing a repeating unit represented by Formula (1) and Formula (2).

In formula (1), R ₁ represents hydrogen or a CH ₃ group.

In formula (1), _{R 2} represents an alkyl group having 2 to 18 carbon atoms.

As R ₂ , for example, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, isopropyl group, isobutyl group, s-butyl group And linear alkyl groups such as t-butyl group, s-pentyl group and 2-ethylhexyl group, and branched alkyl groups.

In formula (2), R ₃ represents hydrogen or a CH ₃ group.

  In formula (2), a and b each independently represent 1 or 2 and c represents 0 or 1.

In formula (2), m represents an integer greater than or equal to n-2, and n represents the number of carbon atoms of the longest alkyl chain in R ₂ in formula (1). Here, when m is an integer less than n-2, photocrosslinking of the resin becomes difficult.

  In the present invention, the content of the repeating unit represented by the formula (1) is preferably 50 to 95% by mole, and more preferably 75 to 95% by mole, from the viewpoint of excellent solubility in lower aliphatic alcohols.

  In the present invention, the repeating unit represented by the formula (2) is a photocrosslinking group, is suitable for shortening the photocrosslinking time, and contains from the viewpoint of excellent solubility in lower aliphatic alcohols. The amount is preferably 5 to 25 mol%.

  And it is preferable that resin of this invention is resin containing 75-95 mol% of repeating units represented by Formula (1), and 5-25 mol% of repeating units represented by Formula (2).

  In the present invention, the molecular weight of the resin having the repeating unit of the above formula (1) and the above formula (2) is not particularly limited, and is, for example, 5000 to 1,000,000 (g / mol). It is preferably 10,000 to 500,000 (g / mol) from the viewpoint of solution viscosity and mechanical strength of the resin.

  There is no restriction | limiting in particular as a manufacturing method of resin of this invention, For example, polymerizing the monomer represented by Formula (3) and Formula (4) by well-known radical polymerization is mentioned.

(In formula (3), R ₁ represents hydrogen or a CH ₃ group, and R ₂ represents an alkyl group having 2 to 18 carbon atoms.)

(In formula (4), R ₃ represents hydrogen or a CH ₃ group, a and b each independently represent 1 or 2, c represents 0 or 1, and m represents an integer of 2 or more. , N represents the number of carbon atoms of the longest alkyl chain in R ₂ in the formula (1).)
For radical polymerization of the monomers represented by the above formulas (3) and (4), 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 particularly limited as long as the above monomers and the polymer of the present invention dissolve, and examples thereof include aromatic solvents such as toluene and xylene, amide solvents such as dimethylformamide, tetrahydrofuran and the like Cyclic ether solvents and the like can be mentioned, and these solvents can also be mixed and used. The polymerization temperature is selected depending on the initiator used but is not particularly limited. As an initiator, any of an azo initiator and a peroxide initiator can be used. The reaction time is set according to the half life of the initiator used and is not limited in any way, but it is 4 to 8 hours from the viewpoint of economy.

  The resin of the present invention can be coated or printed on various substrates in the form of a solution dissolved in a solvent. As the solvent, any solvent that dissolves the resin can be used without any limitation, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-pentanol Aliphatic alcohols such as: ethers such as dibutyl ether and diisobutyl ether; aromatic hydrocarbons such as toluene, xylene, cumene and mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and bromobenzene; methyl Ketones such as isobutyl ketone, ethyl isobutyl ketone, cyclopentanone and cyclohexanone; esters such as n-butyl acetate, isobutyl acetate and propyl propionate; amides such as N-methylpyrrolidone and dimethylformamide; diethylene glycol Glycols such as butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate and the like, and one or more solvents may be used in combination as long as the resin is dissolved. May be Among them, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-pentanol and the like because they can be solution-coated on the organic semiconductor layer Is preferred, and lower aliphatic alcohols having 4 or less carbon atoms are more preferred.

  There are no limitations on the coating or printing method, and examples include spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, Printing can be performed using gravure printing, flexographic printing, screen printing, inkjet printing, letterpress reverse printing, and the like.

When the resin according to the present invention is used as an insulating layer, it can be used in the state in which the insulating layer is formed, and can be used as a photocrosslinked (photocyclized) crosslinked product as required. In the present invention, when the resin is used for photocrosslinking, the resulting insulating layer contains a crosslinked product, which is preferable from the viewpoint of solvent resistance. In the present invention, when the insulating layer is formed and then used without photocrosslinking, the general solvent used for forming the insulating layer exhibits good solubility, and the upper portion of the insulating layer It is necessary that the organic semiconductor layer can be formed using a solvent different from the general-purpose solvent. At this time, when the insulating layer has solvent resistance to the organic semiconductor solution, the insulating layer can be used as it is.

When the resin according to the present invention is used by photocrosslinking, radiation is used for photocrosslinking (photocyclization), and for example, ultraviolet rays having a wavelength of 245 to 350 nm are exemplified. The irradiation dose is appropriately changed depending on the composition of the resin, and, for example, 100 to 1000 mJ / cm ² may be mentioned to prevent a decrease in the degree of crosslinking and to reduce the process time (photocrosslinking time). Preferably, it is 50 to 500 mJ / cm ² . Irradiation of ultraviolet light is usually performed in the atmosphere, but may be performed in an inert gas or under a certain amount of inert gas flow, if necessary. A photosensitizer can be added to accelerate the photocrosslinking reaction, if necessary. The photosensitizer to be used is not particularly limited, and examples thereof include benzophenone compounds, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds and the like, but benzophenone compounds having high compatibility with the resin used in the present invention are preferable. Moreover, the said sensitizer can be used combining 2 or more types as needed.

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

  In addition, the resin of the present invention can be efficiently crosslinked in a short time, and the time required for crosslinking can be made within 5 minutes. In addition, since it is suitable for control of crosslinking time, it is preferable to make the time which crosslinking requires within 1-2 minutes.

  The resin of the present invention can be suitably used as a gate insulating layer of an organic transistor. The organic transistor has a gate insulating layer on a substrate. Further, an organic semiconductor layer is formed on the gate insulating layer, and a source electrode, a drain electrode, and a gate electrode are provided. The resin of the present invention can also be used as a protective layer of an organic semiconductor layer, but in this case, the resin can be used in either uncrosslinked or crosslinked state.

  The organic transistor of the present invention is of the bottom gate-top contact type (A), bottom gate-bottom contact type (B), top gate-top contact type (C), and top gate-bottom contact type (D) shown in FIG. Any element structure may be used. Here, 1 represents an organic semiconductor layer, 2 represents a substrate, 3 represents a gate electrode, 4 represents a gate insulating layer, 5 represents a source electrode, and 6 represents a drain electrode.

  In the organic transistor, the base material that can be used is not particularly limited as long as sufficient flatness for manufacturing the device can be ensured. For example, glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide Inorganic material substrates such as indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; surface-coated non-woven fabrics etc .; composite materials comprising these materials or materials thereof It may be a multi-layered material. The surface of these materials can also be coated to adjust the surface tension.

  Examples of 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, polypropylene Cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), poly (diisopropyl maleate), polyether sulfone, polyphenylene sulfide, polyphenylene ether, Polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elast Mer, styrene block copolymer and the like. In addition, two or more of the above-mentioned plastics can be used as a substrate by laminating them.

  The organic semiconductor that can be used in the present invention is not particularly limited, and any of N-type and P-type organic semiconductors can be used, and can also be used as a bipolar transistor combining N-type and P-type. In addition, any of low molecular weight and high molecular weight organic semiconductors can be used, and these can be used as a mixture. As a specific compound, Formula (F-1)-(F-11) etc. are illustrated, for example.

  In the present invention, as a method of forming an organic semiconductor layer, a method of vacuum depositing an organic semiconductor, or a method of dissolving an organic semiconductor in an organic solvent to apply and print is exemplified. There is no limitation as long as it can be formed. The solution concentration in the case of coating or printing 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 used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the thickness of the layer Therefore, it is preferable that it is 0.5 to 5 weight%. The organic solvent at this time is not particularly limited as long as the organic semiconductor is dissolved at a certain concentration capable of forming a film, and hexane, heptane, octane, decane, dodecane, 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, 1,2,3,4,5,6,7,8,8-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 etc. In order to obtain a film, solvents having a high solvency of organic semiconductor and a boiling point of 100 ° C. or more are suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole And pentylbenzene, tetralin, cyclohexylbenzene and decahydro-2-naphthol are preferable. Moreover, the mixed solvent which mixed 2 or more types of the above-mentioned solvent in a suitable ratio can also be used.

  If necessary, various organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added to the organic semiconductor layer as a solid or as a dispersion liquid in which nanoparticles are dispersed in water or an organic solvent, A polymer solution can be applied to form a protective film. Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied on the present protective film as required.

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

  Further, the method of forming an electrode on the above-mentioned base material, insulating layer or organic semiconductor layer is not particularly limited, and vapor deposition, high frequency sputtering, electron beam sputtering and the like can be mentioned. Method of solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexo printing, screen printing, inkjet printing, letterpress reverse printing, etc. using ink dissolved in organic solvent Can also be adopted.

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

  The organic transistor of the present invention preferably has a threshold voltage of −10.0 V or more and less than 0 V from the viewpoint of practicability 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 practicability of the organic transistor element.

  The organic transistor of the present invention can be suitably used as an electronic device.

  According to the present invention, it becomes possible to provide a resin for forming a photocrosslinkable insulating layer which is soluble in a lower aliphatic alcohol.

FIG. 5 is a view showing a cross-sectional shape of an organic transistor. FIG. 5 is a diagram showing a ¹ H-NMR chart of a resin produced in Example 1.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

  In addition, n-decyl acrylate and n-octyl methacrylate (NOMA) (the following formula (A)) used in the examples can be obtained by the method described in Macromolecules, vol. 39, No. 14, p. 4726, 2006. 9-anthrylmethyl methacrylate (AMMA) (following formula (B)) is anthryl decyl methacrylate (ADMA) (following formula (C)) according to the method described in Macromolecules, 1980, 13: 289 In the method described in Journal of Polymer Science, 2015, 53, 1252, anthryloxy-n-octyl methacrylate (AOOMA) (Formula (D) below) is a Journal of Organic Chemistry. 1983, 48, p. 2779 and Tetrahydrone, 2016, p. Volume 2 was synthesized by the method described page 4303. In addition, 2,6-di-t-butyl-p-cresol (BHT) used a reagent manufactured by Tokyo Kasei Kogyo Co., Ltd., and azoisobutyronitrile (AIBN) used a reagent manufactured by Wako Pure Chemical Industries, Ltd.

<NMR>
¹ H-NMR and ¹³ C-NMR of a deuterated chloroform solvent of the polymer were measured using JNM-ECZ400S FT-NMR (manufactured by Nippon Denshi Co., Ltd.). The chemical structural determination of the polymer, the above equations (1), and the content of the repeating unit represented by the formula (2) (mol%), respectively, as _{U 1,} and _{U ^2,} 1 H-NMR measurement It calculated | required by following formula (a)-(b) using the integral intensity | strength of the peak obtained by these.

U ₂ = 2 (1 + c) I ₁ / {9 + 2 (a + b)} (a)
U ₁ = 1-U ₂ (b)
(Here, I ₁ represents the sum of integral values of peaks present at δ 7.0 to δ 8.5 ppm, and I ₂ represents the sum of integral values of peaks present at p δ 3.5 to 4.5 pm.)
<Spin coat>
Opticoat MS-A100 manufactured by Mikasa Co., Ltd. was used.
<Film thickness measurement>
It measured using contact-type surface profiler (made by Bruker, brand name Dektak XT-E).
<UV irradiation>
Using UV-System, CSN-40A-2 manufactured by GS Yuasa Corporation, UV irradiation was performed under the condition of UV intensity of 4.0 kW.
<Method for evaluating photocrosslinkability>
The film thickness before UV irradiation is T1, and the film after UV irradiation is immersed in toluene for 20 minutes to remove solubles, and the film thickness after drying at 100 ° C. × 10 minutes is T2, T2 / T1 × 100 The residual film rate was determined by (%), and the photocrosslinkability was determined using the residual film rate of 95% or more as a criterion.
<Vacuum deposition>
A small vacuum evaporation apparatus VTR-350M / ERH manufactured by ULVAC KIKO, Inc. was used.
<Evaluation of FET device>
A top gate bottom contact (TGBC) type element which is one form of an organic transistor is manufactured, and a gate voltage is changed by using a semiconductor parameter analyzer 4200-SCS manufactured by Keithley Co. and setting a source-drain voltage to minus 20 volts. The mobility, leakage current, and threshold voltage were evaluated by

Example 1
<Synthesis of resin and evaluation of photocrosslinkability>
In a 20 mL Schlenk tube containing a magnetic stirrer chip, 0.232 g of AAOMA, 0.768 g of NOMA, 6.5 mg of AIBN and 3.9 g of toluene are charged, and AIBN is dissolved by an ultrasonic cleaner to form a uniform solution . The solution was frozen with liquid nitrogen, degassed and dissolved, and this procedure was repeated four times to remove oxygen from the solution. Thereafter, nitrogen is rapidly introduced into the Schlenk tube, the contents are dissolved in a water bath, the precipitate is dissolved using an ultrasonic cleaner, and then polymerization is carried out at 60 ° C. for 8 h under stirring. Stopper (methylene chloride of BHT Solution was added. Under stirring, the reaction solution was poured into 200 mL of hexane to precipitate a pale yellow polymer. The obtained polymer was dissolved in 5 g of methylene chloride and again poured into 15 mL of hexane for reprecipitation purification. The precipitated polymer was filtered by suction with a cellulose filter, washed with hexane, and then dried under reduced pressure at 40 ° C. to obtain 0.3 g of resin 1.

As a result of analysis by ¹ H-NMR (FIG. 2), the obtained resin 1 (the following formula) (n = 8) has 86.4 mol of structural units represented by the formula (1) and the formula (2) respectively % And 13.6 mol% were confirmed.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.27 (brs, aromatic), δ 8.20 (brs, aromatic), δ 7.45 (brs, aromatic), δ 4.17 (brs, -OCH ₂₎ −), Δ 3.92 (brs, -OCH _2- ), δ 2.2 to 0.7 (m, -CH _2- ,), δ 1.59 (s, -CH ₃ )
A toluene solution (5 wt%) of resin 1 is spin-coated on a washed and dried 30 × 30 mm ² glass (substrate) (Eglex G manufactured by Corning) at 500 rpm × 5 seconds, 1000 rpm × 20 seconds, 100 ° C. After drying for 10 minutes, UV light of 500 mJ / cm ² was applied (room temperature) to evaluate the photocrosslinkability. The evaluation results are shown in Table 1.

It was confirmed that the resin 1 crosslinks with a low UV irradiation amount and is excellent in photocrosslinkability.
<Preparation and Evaluation of Organic Transistor Device>
0.2 g of dichlorodiparaxylylene (trade name DPX-C, manufactured by Nippon Parylene Co., Ltd.) on a washed and dried 30 × 30 mm ² glass (base material) (EAGLE XG manufactured by Corning, Inc.) Vacuum deposition using the name PDS 2010) to form a planarized layer of poly (parachloroxylylene). Further, a silver electrode was vacuum deposited on the planarizing layer to form an electrode having a thickness of 30 nm. Then, it was immediately immersed in a 2-propanol solution of 30 mmol / L of pentafluorobenzenethiol, taken out after 5 minutes, washed with 2-propanol and blow-dried. A 0.2 wt% toluene solution of 2,7-di (n-hexyl) dithienobenzodithiophene is drop-cast onto a substrate on which an electrode is formed, and naturally dried at room temperature (25 ° C.) to obtain an organic semiconductor layer. It formed. Furthermore, an n-butanol solution (5 wt%) of resin 1 is spin coated on the organic semiconductor layer under conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds, dried at 100 ° C. for 10 minutes, and then 500 mJ / cm ² ultraviolet light is applied. It irradiated and irradiated (room temperature) and bridge | crosslinked, and formed the gate insulating layer with a film thickness of 590 nm. Further, a silver electrode was vacuum deposited on the gate insulating layer to fabricate a top gate bottom contact (TGBC) type device which is one mode of an organic transistor. The evaluation results and the like of the manufactured organic transistor are shown in Table 1.

  It was confirmed that the manufactured organic transistor had a small leakage current, and the insulating layer had excellent insulation.

(Example 2)
<Synthesis of resin and evaluation of photocrosslinkability>
0.31 g of Resin 2 was obtained in the same manner as in Example 1 except that 0.299 g of AOOMA, 0.711 g of NOMA, and 6.3 mg of AIBN were used, and the polymerization time was 5 hours.

As a result of analysis by ¹ H-NMR, the obtained resin 2 (the following formula) (n = 8) has 78.1 mol% and 21 of structural units represented by the formula (1) and the formula (2), respectively. It was confirmed to have 9 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.27 (brs, aromatic), δ 8.20 (brs, aromatic), δ 7.45 (brs, aromatic), δ 4.17 (brs, -OCH ₂₎ −), Δ 3.92 (brs, -OCH _2- ), δ 2.2 to 0.7 (m, -CH _2- ,), δ 1.59 (s, -CH ₃ )
The photocrosslinkability was evaluated in the same manner as in Example 1 except that Resin 1 was changed to Resin 2. The evaluation results are shown in Table 1 together.

It was confirmed that the resin 2 crosslinks with a low UV irradiation amount and is excellent in photocrosslinkability.
<Preparation and Evaluation of Organic Transistor Device>
A top gate bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 1 except that Resin 1 was changed to Resin 2. The evaluation results etc. are shown in Table 1 together.

  It was confirmed that the manufactured organic transistor had a small leakage current, and the insulating layer had excellent insulation.

(Example 3)
<Synthesis of resin and evaluation of photocrosslinkability>
0.22 g of resin 3 was obtained in the same manner as in Example 1 except that 0.193 g of AOOMA, 0.811 g of NOMA, and 6.7 mg of AIBN were used, and the polymerization time was 5 hours.

As a result of analysis by ¹ H-NMR, the obtained resin 3 (the following formula) (n = 8) has 87.9 mol% of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) It was confirmed to have .1 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.27 (brs, aromatic), δ 8.20 (brs, aromatic), δ 7.45 (brs, aromatic), δ 4.17 (brs, -OCH ₂₎ −), Δ 3.92 (brs, -OCH _2- ), δ 2.2 to 0.7 (m, -CH _2- ,), δ 1.59 (s, -CH ₃ )
The photocrosslinkability was evaluated in the same manner as in Example 1 except that Resin 1 was changed to Resin 3. The evaluation results are shown in Table 1 together.

It was confirmed that the resin 3 was crosslinked at a low UV irradiation amount and was excellent in photocrosslinkability.
<Preparation and Evaluation of Organic Transistor Device>
A top gate bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 1 except that Resin 1 was changed to Resin 3. The evaluation results etc. are shown in Table 1 together.

It was confirmed that the manufactured organic transistor had a small leakage current, and the insulating layer had excellent insulation.

(Example 4)
<Synthesis of resin and evaluation of photocrosslinkability>
AOOMA was changed to ADMA, 0.32 g of resin 4 was used in the same manner as in Example 1 except that the addition amount was 0.25 g, NOMA was 1.75 g, AIBN was 13.5 mg, and the polymerization time was 8 hours. Obtained.

As a result of analysis by ¹ H-NMR, the obtained resin 4 (the following formula) (n = 8) has 87.5% by mole of the structural unit represented by formula (1) and formula (2), and 12 It was confirmed to have .5 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.29 (brs, aromatic), δ 8.23 (brs, aromatic), δ 7.96 (brs, aromatic), δ 7.44 (brs, aromatic) , Δ 4.12 (brs, -OCH _2- ), δ 3.53 (brs, -OCH _2- ), δ 2.0 to 0.7 (m, -CH _2- , -CH ₃ )
The photocrosslinkability was evaluated in the same manner as in Example 1 except that Resin 1 was changed to Resin 4. The evaluation results are shown in Table 1 together.

It was confirmed that the resin 4 crosslinks with a low UV irradiation amount and is excellent in photocrosslinkability.
<Preparation and Evaluation of Organic Transistor Device>
A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 1 except that Resin 1 was changed to Resin 4. The evaluation results etc. are shown in Table 1 together.

  It was confirmed that the produced OFET had a small leakage current, and the insulating layer had excellent insulation.

(Example 5)
<Synthesis of resin and evaluation of photocrosslinkability>
AOOMA was changed to ADMA, and 0.25 g of resin 5 was used in the same manner as in Example 1 except that the amount added was 0.182 g, NOMA 1.818 g, AIBN 13.8 mg, and the polymerization time was 3 hours. Obtained.

As a result of analysis by ¹ H-NMR, the obtained resin 5 (the following formula) (n = 8) has 95.0 mol% and 5 of the structural units represented by the formula (1) and the formula (2), respectively. It was confirmed to have .0 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.29 (brs, aromatic), δ 8.23 (brs, aromatic), δ 7.96 (brs, aromatic), δ 7.44 (brs, aromatic) , Δ 4.12 (brs, -OCH _2- ), δ 3.53 (brs, -OCH _2- ), δ 2.0 to 0.7 (m, -CH _2- , -CH ₃ )
The photocrosslinkability was evaluated in the same manner as in Example 1 except that Resin 1 was changed to Resin 5. The evaluation results are shown in Table 1 together.

It was confirmed that the resin 5 crosslinks with a low UV irradiation amount and is excellent in photocrosslinkability.
<Preparation and Evaluation of Organic Transistor Device>
A top gate bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 1 except that Resin 1 was changed to Resin 5. The evaluation results etc. are shown in Table 1 together.

  It was confirmed that the produced OFET had a small leakage current, and the insulating layer had excellent insulation.

(Comparative example 1)
<Synthesis of resin and evaluation of photocrosslinkability>
In a 20 mL Schlenk tube containing a magnetic stirrer chip, 2.0 g of NOMA, 16.0 mg of AIBN, and 6.0 g of toluene were charged, and AIBN was dissolved by an ultrasonic cleaner to obtain a uniform solution. The solution was frozen with liquid nitrogen, degassed and dissolved, and this procedure was repeated four times to remove oxygen from the solution. Thereafter, nitrogen is rapidly introduced into the Schlenk tube, the contents are dissolved in a water bath, the precipitate is dissolved using an ultrasonic cleaner, and polymerization is carried out at 70 ° C. for 5 h under stirring. Stopper (methylene chloride of BHT Solution was added. Under stirring, the reaction solution was poured into 200 mL of hexane to precipitate a pale yellow polymer. The obtained polymer was dissolved in 5 g of methylene chloride and again poured into 15 mL of hexane for reprecipitation purification. The precipitated polymer was filtered by suction with a cellulose filter, washed with hexane and then dried under reduced pressure at 40 ° C. to obtain 0.3 g of poly (n-octyl methacrylate) (Resin 6).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.92 (brs, -OCH 2-), δ 1.9 to 0.9 (m, -CH _2- , -CH ₃ )
The photocrosslinkability was evaluated in the same manner as in Example 1 except that Resin 1 was changed to Resin 6. The evaluation results and the like are shown in Table 1, but it was confirmed that the resin 6 was dissolved in toluene and was not photocrosslinked.
<Preparation and Evaluation of Organic Transistor Device>
A top gate bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 1 except that Resin 1 was changed to Resin 6. Since the resin 6 was not crosslinked by ultraviolet light, it was confirmed that the flatness of the film surface was lost by the heat at the time of vacuum deposition of the source electrode and the drain electrode. The evaluation results etc. are shown in Table 1, but the manufactured organic transistor has large leakage current, low mobility and high threshold voltage, and the organic transistor performance is inferior to Examples 1 to 5, and resin It was confirmed that No. 6 had insufficient performance as an insulating layer.

(Comparative example 2)
<Synthesis of resin>
The resin was prepared in the same manner as in Example 1 except that AAOMA was changed to AMMA, the addition amount was 0.476 g, NOMA was 1.524 g, AIBN was 4.8 mg, toluene 8 g, and the polymerization time was 7.5 hours. 0.13 g of 7 was obtained.

  As a result of analysis by 1 H-NMR, the obtained resin 7 (the following formula) (n = 8) has 92.2 mol% of the structural units represented by the formula (1) and the formula (2), respectively, and It confirmed that it had 8 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.49 (brs, aromatic), δ 8.39 (brs, aromatic), δ 8.31 (brs, aromatic), δ 7.59 (brs, aromatic) , Δ 7.49 (brs, aromatic), δ 3.92 (brs, -OCH _2- ), δ 2.0 to 0.8 (m, -CH _2- , -CH ₃ )
<Preparation and Evaluation of Organic Transistor Device>
Although the resin 7 was not dissolved in n-butanol, the resin 7 was applied as a toluene solution on the organic semiconductor layer, but the organic semiconductor layer was dissolved, making it impossible to produce a top gate bottom contact (TGBC) type organic transistor. It was confirmed that it could not be used as an insulating layer for TGBC.

(Comparative example 3)
<Synthesis of resin>
The resin was prepared in the same manner as in Example 1 except that AAOMA was changed to AMMA, and the amount added was 2.384 g, NOMA 7.633 g, AIBN 72.6 mg, toluene 30 g, and the polymerization time was 3.5 hours. 1.9 g of 8 was obtained.

As a result of analysis by ¹ H-NMR, the obtained resin 8 (the following formula) (n = 8) has 74.6 mol% and 25 of structural units represented by the formula (1) and the formula (2), respectively. It was confirmed to have .4 mol%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.49 (brs, aromatic), δ 8.39 (brs, aromatic), δ 8.31 (brs, aromatic), δ 7.59 (brs, aromatic) , Δ 7.49 (brs, aromatic), δ 3.92 (brs, -OCH 2-), δ 2.0 to 0.8 (m, -CH _2- , -CH ₃ )
<Preparation and Evaluation of Organic Transistor Device>
Since the resin 8 was not dissolved in n-butanol, it was coated on the organic semiconductor layer as a toluene solution, but the organic semiconductor layer was dissolved, and a top gate bottom contact (TGBC) type organic transistor could not be produced. The It was confirmed that the resin 8 can not be used as an insulating layer for TGBC.

  It is possible to provide a resin suitable for forming an insulating layer for high quality organic transistor devices that can be manufactured by printed electronics technology.

(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 (5)

Resin containing the repeating unit represented by Formula (1) and Formula (2).
(In formula (1), R ₁ represents hydrogen or a CH ₃ group, and R ₂ represents an alkyl group having 2 to 18 carbon atoms.)
(In formula (2), R ₃ represents hydrogen or a CH ₃ group, a and b each independently represent 1 or 2, c represents 0 or 1, and m represents an integer of 2 or more. , N represents the number of carbon atoms of the longest alkyl chain in R ₂ in the formula (1).) The resin according to claim 1, comprising 5 to 25 mol% of the repeating unit represented by the formula (2). An insulating layer comprising the crosslinked product of the resin according to claim 1 or 2. An organic transistor comprising the insulating layer according to claim 3 as a gate insulating layer. An electronic device comprising the organic transistor according to claim 4.