WO2012108326A1

WO2012108326A1 - Light and heat energy cross-linkable organic thin film transistor insulation layer material

Info

Publication number: WO2012108326A1
Application number: PCT/JP2012/052356
Authority: WO
Inventors: 公矢作
Original assignee: 住友化学株式会社
Priority date: 2011-02-07
Filing date: 2012-02-02
Publication date: 2012-08-16
Also published as: TW201246553A; JP2012164805A

Abstract

The problem addressed by the present invention is to provide an organic thin film transistor insulation layer material capable of producing an organic thin film transistor having low hysteresis and having a threshold voltage with a low absolute value. The problem is solved by an organic thin film transistor insulation layer material containing a polymer compound (A) which has a repeating unit having a substituted maleimide group and has a repeating unit containing a first functional group, said first functional group being a functional group which generates a second functional group which reacts with active hydrogen through the action of electromagnetic radiation or heat.

Description

Light and thermal energy crosslinkable organic thin film transistor insulating layer material

The present invention relates to a material suitable for forming an insulating layer of an organic thin film transistor.

Organic thin-film transistors can be manufactured at a lower temperature than inorganic semiconductors, so plastic substrates and films can be used as their substrates, and by using such substrates, elements that are more flexible, lighter and less fragile than transistors made of inorganic semiconductors. Can be obtained. In some cases, an element can be manufactured by application of a solution containing an organic material or film formation using a printing method, and a large number of elements can be manufactured on a large-area substrate at low cost.

Furthermore, since there are a wide variety of materials that can be used for the study of transistors, if materials having different molecular structures are used for the study, elements having a wide range of characteristic variations can be manufactured.

In a field effect organic thin film transistor which is a kind of organic thin film transistor, a voltage applied to a gate electrode acts on a semiconductor layer through a gate insulating layer to control on / off of a drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer.

In addition, organic semiconductor compounds used in the manufacture of field effect organic thin film transistors are easily affected by the environment such as humidity and oxygen, and the transistor characteristics are likely to deteriorate over time due to humidity, oxygen, and the like.

Therefore, in the bottom gate type organic thin film transistor element structure in which the organic semiconductor compound is exposed, it is essential to form an overcoat layer covering the entire element structure to protect the organic semiconductor compound from contact with the outside air. On the other hand, in the top gate type organic thin film transistor device structure, the organic semiconductor compound is coated and protected by a gate insulating layer.

Thus, an insulating layer material is used to form an overcoat layer, a gate insulating layer, and the like that cover the organic semiconductor layer in the organic thin film transistor. In the present specification, an insulating layer or an insulating film of an organic thin film transistor such as the overcoat layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer. A material used for forming the organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material. In addition, the material here is a concept including an amorphous material such as a polymer compound, a composition containing the polymer compound, a resin, and a resin composition.

The organic thin film transistor insulating layer material is required to have excellent insulating properties and excellent dielectric breakdown strength when formed into a thin film. In particular, in a bottom-gate field effect transistor, a semiconductor layer is formed so as to overlap with a gate insulating layer. Therefore, the organic thin film transistor gate insulating layer material has an affinity with the organic semiconductor for forming an interface closely adhered to the organic semiconductor, and the organic semiconductor layer side surface of the film formed from the organic thin film transistor gate insulating layer material is flat. It is required to be.

As a technology that meets such a requirement, Patent Document 1 describes that an epoxy resin and a silane coupling agent are used in combination as an organic thin film transistor gate insulating layer material. In this technique, a hydroxyl group produced during the curing reaction of an epoxy resin is reacted with a silane coupling agent. This is because the hydroxyl group enhances the hygroscopicity of the gate insulating layer material and impairs the stability of the transistor performance.

Non-Patent Document 1 describes that a resin obtained by thermally cross-linking polyvinylphenol and a melamine compound is used for the gate insulating layer. In this technique, the hydroxyl group contained in polyvinylphenol is removed by crosslinking with a melamine compound, and at the same time the film strength is increased. The pentacene TFT having this gate insulating layer has a small hysteresis and exhibits durability against gate bias stress.

Non-Patent Document 2 describes that polyvinyl gate and a copolymer obtained by copolymerizing vinyl phenol and methyl methacrylate are used for the gate insulating layer. In this technique, the hydroxyl group of vinylphenol interacts with the carbonyl group of methyl methacrylate to reduce the polarity of the entire film. The pentacene TFT having this gate insulating layer has a small hysteresis and exhibits stable electrical characteristics.

JP2007-305950A

However, in consideration of practical use of a light-emitting element such as an organic electroluminescence element (organic EL element), it is necessary to further improve the operation accuracy of the organic thin film transistor. The organic thin film transistor having the conventional gate insulating layer has a threshold voltage ( The absolute value and hysteresis of Vth) are large.

An object of the present invention is to provide an organic thin film transistor insulating layer material capable of producing an organic thin film transistor having a small absolute value of threshold voltage and small hysteresis.

In view of the above, as a result of various studies, the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor are reduced by forming a gate insulating layer using a specific resin composition capable of forming a crosslinked structure. As a result, the inventors have found out that the present invention can be achieved.

That is, the present invention has the formula (1)

[Wherein R ₂ represents a hydrogen atom or a methyl group. R ₃ and R ₄ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. The carbon atom in R ₃ and the carbon atom in R ₄ may be bonded to form a 5-membered ring or a 6-membered ring. R _bb represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. c represents an integer of 0 or 1. ]
And a second functional group containing a first functional group, and the first functional group generates a second functional group that reacts with active hydrogen by the action of electromagnetic waves or heat. The present invention provides an organic thin film transistor insulating layer material containing a polymer compound (A) which is a functional group.

In one certain form, the said high molecular compound (A) is further Formula (2).

[Wherein, R ₁ represents a hydrogen atom or a methyl group. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. u represents an integer of 0 or 1, and b represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of Rf, they may be the same or different. ]
It has the repeating unit represented by these.

In one embodiment, the first functional group is at least one group selected from the group consisting of an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent.

In one embodiment, the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula (3):

(3)

[Wherein, Xa represents an oxygen atom or a sulfur atom, and R ₅ and R ₆ are the same or different and represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

In one embodiment, the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula (4):

(4)

[Wherein, Xb represents an oxygen atom or a sulfur atom, and R ₇ to R ₉ are the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

In one embodiment, the polymer compound (A) further includes two or more structural units having one active hydrogen or a structural unit having two or more active hydrogens.

Further, the present invention further includes at least one selected from the group consisting of an active hydrogen compound which is a low molecular compound containing two or more active hydrogens and an active hydrogen compound which is a polymer compound containing two or more active hydrogens. The organic thin-film transistor insulating layer material containing the active hydrogen compound is provided.

The present invention also includes a step of applying a liquid containing the organic thin film transistor insulating layer material to a substrate to form a coating layer on the substrate; and a step of irradiating the coating layer with an electromagnetic wave or an electron beam;
And a method for forming an organic thin film transistor insulating layer including the same.

The present invention also includes a step of applying a liquid containing the organic thin film transistor insulating layer material to a base material to form a coating layer on the base material;
Irradiating the coating layer with electromagnetic waves or electron beams; and applying heat to the coating layer;
And a method for forming an organic thin film transistor insulating layer including the same.

In one embodiment, the electromagnetic wave is ultraviolet light.

The present invention also provides an organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material.

In one embodiment, the organic thin film transistor insulating layer is a gate insulating layer.

The present invention also provides a display member comprising the organic thin film transistor.

The present invention also provides a display including the display member.

An organic thin film transistor having an insulating layer formed using the organic thin film transistor insulating layer material of the present invention has a small absolute value of threshold voltage and a small hysteresis.

It is a schematic cross section which shows the structure of the bottom gate top contact type organic thin-film transistor which is one Embodiment of this invention. It is a schematic cross section which shows the structure of the bottom gate bottom contact type organic thin-film transistor which is other embodiment of this invention.

In the present specification, “polymer compound” refers to a compound having a structure in which a plurality of the same structural units are repeated in the molecule, and includes a so-called dimer. On the other hand, the “low molecular compound” means a compound that does not have the same structural unit repeatedly in the molecule.

<Polymer Compound (A)>
The organic thin film transistor insulating layer material of the present invention includes a polymer compound, and the polymer compound has a plurality of functional groups that absorb the energy of electromagnetic waves or the energy of electron beams to cause a dimerization reaction. When it acts, it has a plurality of first functional groups that generate a second functional group that reacts with active hydrogen. The functional group that absorbs electromagnetic energy or electron beam energy to cause a dimerization reaction is referred to as a “photodimerization reactive group” in this specification. In the present specification, “active hydrogen” means a hydrogen atom bonded to an oxygen atom, a sulfur atom or a nitrogen atom.

In one form, the photodimerization reactive group is a functional group that can perform a concerted reaction when absorbing light energy or electron beam energy. Functional groups that can perform a concerted reaction can be dimerized by cycloaddition with each other to form a crosslinked structure inside the insulating layer.

The electromagnetic wave absorbed by the photodimerization reactive group is preferably low energy, so that when the organic thin film transistor insulating layer material is formed by the photopolymerization method, the photodimerization reactive group may also react. . A preferable electromagnetic wave to be absorbed by the photodimerization reactive group is ultraviolet light, for example, light having a wavelength of 400 nm or less, preferably 150 to 390 nm, more preferably 280 to 380 nm.

“Dimerization” here means that two molecules of an organic compound are chemically bonded. The molecules to be bound may be the same or different. The chemical structures of the functional groups involved in dimerization in the two molecules to be dimerized may be the same or different. However, it is preferable that the functional group has a structure and a combination that cause a photodimerization reaction even when a reaction aid such as a catalyst and an initiator is not used. This is because contact with the residue of the reaction aid may cause deterioration of surrounding organic materials.

The first functional group contained in the polymer compound does not react with active hydrogen, but when an electromagnetic wave or heat acts on the first functional group, a second functional group is generated and reacts with active hydrogen. That is, the first functional group is deprotected by electromagnetic waves or heat to generate a second functional group that reacts with active hydrogen. The second functional group reacts with and binds to the active hydrogen-containing group of the active hydrogen compound (E), so that a crosslinked structure can be formed inside the insulating layer. In the present specification, the “active hydrogen compound” means a compound having one or more active hydrogens.

The second functional group is protected (blocked) in the step of forming the gate insulating layer until electromagnetic waves or heat is applied, and is present in the organic thin film transistor insulating layer material as the first functional group. As a result, the storage stability of the organic thin film transistor insulating layer material is improved.

For example, a polymer compound containing a repeating unit having a photodimerization reactive group and a repeating unit having the first functional group corresponds to the polymer compound.

The repeating unit having a photodimerization reactive group is preferably a repeating unit represented by the above formula (1). The polymer compound contained in the organic thin film transistor insulating layer material of the present invention is preferably a polymer compound having a repeating unit represented by the formula (1) and a repeating unit containing a first functional group. Such a polymer compound is referred to as a polymer compound (A).

In formula (1), R ₂ represents a hydrogen atom or a methyl group. In some one aspect, R ₂ is a methyl group.

In the formula (1), R ₃ and R ₄ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be saturated or unsaturated.

Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon having 3 to 20 carbon atoms. Group, aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably linear hydrocarbon group having 1 to 6 carbon atoms, branched hydrocarbon group having 3 to 6 carbon atoms, or 3 to 6 carbon atoms. And an aromatic hydrocarbon group having 6 to 20 carbon atoms.

In a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon group having 3 to 20 carbon atoms, the hydrogen atoms contained in these groups are substituted with fluorine atoms. May be.

In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

Specific examples of the monovalent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, cyclopropyl group, Cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl group, trifluoromethyl group, trifluoroethyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenyl group, trimethylphenyl group , Ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, ethenylnaphthyl group, methylanthryl group, ethylanthryl group, Chloroph Alkenyl groups include bromophenyl group.

As the monovalent organic group having 1 to 20 carbon atoms, an alkyl group is preferable.

The carbon atom in R ₃ and the carbon atom in R ₄ may be bonded to form a 5-membered ring or a 6-membered ring. Examples of the 5-membered ring include a cyclopentene ring. Examples of the 6-membered ring include a cyclohexene ring.

In one certain form, R < ₃ > and R < ₄ > are the same or different, and are groups selected from the group which consists of a methyl group and an ethyl group.

In formula (1), R _bb represents a linking moiety that links the main chain and the side chain and may have a fluorine atom. The connecting portion may be a divalent group having a structure that does not exhibit reactivity under environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention. Specific examples of the linking moiety include a bond composed of a divalent organic group having 1 to 20 carbon atoms, an ether bond (—O—), a ketone bond (—CO—), an ester bond (—COO—, —OCO—). Amide bond (—NHCO—, —CONH—), urethane bond (—NHCOO—, —OCONH—), and a combination of these bonds. c represents an integer of 0 or 1. In one certain form, c is 1.

The divalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. For example, a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, and a divalent cyclic hydrocarbon group having 3 to 20 carbon atoms And a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like. Among them, a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms. In addition, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like is preferable.

Specific examples of the divalent aliphatic hydrocarbon group and the divalent cyclic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, and dimethylpropylene. Group, cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group.

Specific examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, ethylenephenylene group, diethylenephenylene group, triethylenephenylene group, Examples include propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and ethylanthrylene group.

A preferred example of the photodimerization reactive group is a group represented by the formula (5), in which the hydrogen atom at the 3-position and the hydrogen atom at the 4-position of the maleimide group are each substituted with an alkyl group or an aryl group. In the formula (5), R ′ is preferably a propane-1,3-diyl group or a butane-1,4-diyl group.

(5)

In formula (5), R ′ represents an alkanediyl group.

When the photodimerization reactive group is a group in which the hydrogen atom at the 3-position and the hydrogen atom at the 4-position of the maleimide group are each substituted with an alkyl group or an aryl group, or a group represented by the formula (5), an ultraviolet ray or an electron beam is used. When irradiated, a 2 + 2 cyclization reaction occurs and the organic thin film transistor insulating layer material is crosslinked.

In addition, preferable examples of the first functional group include an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent.

The isocyanato group blocked with the blocking agent or the isothiocyanato group blocked with the blocking agent is an isocyanate group or an isocyanate group having only one active hydrogen capable of reacting with an isocyanato group or an isothiocyanato group, or It can be produced by reacting with an isothiocyanato group.

The blocking agent is preferably one that dissociates at a temperature of 170 ° C. or lower even after reacting with an isocyanato group or an isothiocyanato group. Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oxime compounds. , Amine compounds, imine compounds, bisulfites, pyridine compounds, and pyrazole compounds. These blocking agents may be used alone or in combination of two or more. Preferable blocking agents include oxime compounds and pyrazole compounds.

Specific blocking agents are exemplified below. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, and cyclohexanol. Examples of phenolic compounds include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of mercaptan compounds include butyl mercaptan and dodecyl mercaptan. Examples of the acid amide compounds include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Examples of the acid imide compounds include succinimide and maleic imide. Examples of the imidazole compound include imidazole and 2-methylimidazole.
Examples of the urea compound include urea, thiourea, and ethylene urea. Examples of the amine compound include diphenylamine, aniline, and carbazole. Examples of the imine compound include ethyleneimine and polyethyleneimine. An example of a bisulfite is sodium bisulfite. Examples of pyridine compounds include 2-hydroxypyridine and 2-hydroxyquinoline. Examples of oxime compounds include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of the pyrazole compound include 3,5-dimethylpyrazole and 3,5-diethylpyrazole.

The isocyanato group or isothiocyanato group blocked with a blocking agent that may be used in the present invention is preferably a group represented by the above formula (3) or a group represented by the above formula (4).

In the formulas (3) and (4), Xa represents an oxygen atom or a sulfur atom, Xb represents an oxygen atom or a sulfur atom, and R ₅ to R ₉ are the same or different and represent a hydrogen atom or a carbon number. 1 to 20 monovalent organic groups are represented. The definition and specific examples of the monovalent organic group are the same as the definition and specific examples of the monovalent organic group described above.

In one certain form, R ₅ to R ₉ are hydrogen atoms.

Examples of the isocyanato group blocked with a blocking agent include O- (methylideneamino) carboxyamino group, O- (1-ethylideneamino) carboxyamino group, O- (1-methylethylideneamino) carboxyamino group, O— [1-methylpropylideneamino] carboxyamino group, (N-3,5-dimethylpyrazolylcarbonyl) amino group, (N-3-ethyl-5-methylpyrazolylcarbonyl) amino group, (N-3,5-diethyl) And pyrazolylcarbonyl) amino group, (N-3-propyl-5-methylpyrazolylcarbonyl) amino group, and (N-3-ethyl-5-propylpyrazolylcarbonyl) amino group.

Examples of the isothiocyanato group blocked with a blocking agent include an O- (methylideneamino) thiocarboxyamino group, an O- (1-ethylideneamino) thiocarboxyamino group, and an O- (1-methylethylideneamino) thiocarboxyamino group. , O- [1-methylpropylideneamino] thiocarboxyamino group, (N-3,5-dimethylpyrazolylthiocarbonyl) amino group, (N-3-ethyl-5-methylpyrazolylthiocarbonyl) amino group, (N -3,5-diethylpyrazolylthiocarbonyl) amino group, (N-3-propyl-5-methylpyrazolylthiocarbonyl) amino group, and (N-3-ethyl-5-propylpyrazolylthiocarbonyl) amino group.
The first functional group is preferably an isocyanato group blocked with a blocking agent.

The polymer compound (A) comprises, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (1) and a polymerizable monomer containing the first functional group as a photopolymerization initiator or heat. It can manufacture by the method of copolymerizing using a polymerization initiator.

Polymerization of the polymerizable monomer may be performed by a method commonly used by those skilled in the art. As a method for polymerizing a polymerizable monomer, for example, a method in which a polymerizable monomer and a polymerization initiator are dissolved in a suitable solvent, dissolved oxygen in the resulting solution is replaced with an inert gas, and then heated or irradiated for a certain time. Is exemplified.

Examples of the polymerizable monomer that is a raw material for the repeating unit represented by the above formula (1) include N- (3′-methacryloyloxypropyl) -3,4-dimethylmaleimide, N- (3′-methacryloyloxypropyl). ) -1-cyclohexene-1,2-dicarboximide.

Examples of the polymerizable monomer containing the first functional group include a monomer having an isocyanato group blocked with a blocking agent or an isothiocyanate group blocked with a blocking agent and an unsaturated bond. A monomer having an isocyanato group blocked with the blocking agent or an isothiocyanate group blocked with a blocking agent and an unsaturated bond includes an isocyanate group or a compound having an isothiocyanato group and an unsaturated bond, and a blocking agent. It can be produced by reacting. As the unsaturated bond, a double bond is preferable.

Examples of the compound having a double bond and an isocyanato group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl isocyanate.
Examples of the compound having a double bond and an isothiocyanato group include 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl isothiocyanate.

As the blocking agent contained in the polymerizable monomer, the above blocking agent can be suitably used. In the production of a monomer having an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent and an unsaturated bond, an organic solvent, a catalyst or the like can be added as necessary.

Examples of the monomer having an isocyanate group blocked with the blocking agent and a double bond include 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate, 2- [N- [ 1 ', 3'-dimethylpyrazolyl] carbonylamino] ethyl-methacrylate.

Examples of monomers having an isothiocyanate group and a double bond blocked with the blocking agent include 2- [O- [1′-methylpropylideneamino] thiocarboxyamino] ethyl-methacrylate, 2- [N— And [1 ′, 3′-dimethylpyrazolyl] thiocarbonylamino] ethyl-methacrylate.

Examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy- 2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, -Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, benzyl dimethyl Examples include carbonyl compounds such as luketal, benzyl diethyl ketal and diacetyl, sulfur compounds such as anthraquinone derivatives such as methyl anthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, thioxanthone derivatives, diphenyl disulfide and dithiocarbamate. .

When light energy is used as the energy for initiating copolymerization, the wavelength of light irradiated to the polymerizable monomer is 360 nm or more, preferably 360 to 450 nm.

The thermal polymerization initiator may be any compound that serves as a radical polymerization initiator. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylpropane) ), Azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyl peroxide Oxide, benzoyl peroxide, 2,4-dichlorobenzoyl paro Diacyl peroxides such as sid, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide Hydroperoxides such as oxide and tert-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, and tris (tert-butylperoxy) triazine 1,1-di-tert-butylperoxycyclohexane, peroxyketals such as 2,2-di (tert-butylperoxy) butane, tert-butylperoxypivalate, tert-butylperoxy -2-Ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3,5,5- Alkyl peresters such as trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate And peroxycarbonates such as tert-butylperoxyisopropyl carbonate.

The polymer compound (A) used in the present invention polymerizes a polymerizable monomer other than a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (1) and a polymerizable monomer containing the first functional group. Sometimes it may be added and manufactured.

Additional polymerizable monomers used include, for example, acrylic acid esters and derivatives thereof, methacrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof. Organic carboxylic acid vinyl esters and derivatives thereof, organic carboxylic acid allyl esters and derivatives thereof, fumaric acid dialkyl esters and derivatives thereof, maleic acid dialkyl esters and derivatives thereof, itaconic acid dialkyl esters and derivatives thereof, organic carboxylic acids Examples thereof include N-vinylamide derivatives of acids, terminal unsaturated hydrocarbons and derivatives thereof, and organic germanium derivatives containing unsaturated hydrocarbon groups.

The type of polymerizable monomer used additionally is appropriately selected according to the characteristics required for the insulating layer. From the viewpoint of excellent durability against solvents and reducing the hysteresis of organic thin film transistors, monomers that have high molecular density and form a hard film are selected in films containing these compounds, such as styrene and styrene derivatives. . In addition, from the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode or the surface of the substrate, the polymer compound (A) is made plastic such as methacrylic acid esters and derivatives thereof, acrylic acid esters and derivatives thereof. The monomer to be imparted is selected.

As acrylic acid esters and derivatives thereof, monofunctional acrylates and polyfunctional acrylates can be used although the amount of use is limited. As such monofunctional acrylates and polyfunctional acrylates, For example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, acrylic acid-sec-butyl, hexyl acrylate, octyl acrylate, acrylic 2-ethylhexyl acid, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, Acrylic acid -Hydroxybutyl, 2-hydroxyphenylethyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylol Propane triacrylate, pentaerythritol pentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3-perfluorobutyl -2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl Acrylate, 2- (perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 3- ( Perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro -5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H-1- (trifluoromethyl) Examples thereof include trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-acryloylmorpholine.

As the methacrylic acid esters and derivatives thereof, monofunctional methacrylates and polyfunctional methacrylates can be used although the amount of use is limited. Such monofunctional methacrylates and Examples of the functional methacrylate include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-sec. -Butyl, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylate 2-hydroxyethyl, 2-hydroxypropyl taacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, 2,2,2-trifluoroethyl methacrylate Acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 3-perful Robutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl- 2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- (perfluoro-5-methylhexyl) -2 -Hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate Acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H-1- (trifluoromethyl) trifluoro Examples thereof include ethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-acryloylmorpholine.

Examples of styrene and its derivatives include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene. 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m -Ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydro Cystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl Toluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl -Α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4-aminostyrene.

Examples of organic carboxylic acid vinyl esters and derivatives thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate.

Examples of allyl esters of organic carboxylic acids and derivatives thereof include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

Examples of dialkyl esters of fumaric acid and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2 fumarate -Ethylhexyl, dibenzyl fumarate.

Examples of dialkyl esters of maleic acid and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2 maleate -Ethylhexyl, dibenzyl maleate.

Examples of dialkyl esters of itaconic acid and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2 itaconate -Ethylhexyl, dibenzyl itaconate.

Examples of N-vinylamide derivatives of organic carboxylic acids include N-methyl-N-vinylacetamide.

Examples of terminal unsaturated hydrocarbons and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and allyl alcohol.

Examples of the organic germanium derivative containing an unsaturated hydrocarbon group include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, and triethylvinylgermanium.

Among these, acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, acrylonitrile, methacrylonitrile, and allyltrimethylgermanium are preferable.

The charged molar ratio of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is 5 mol% or more and 50 mol% or less, preferably 10 mol% or more and 45 mol% in all monomers involved in the polymerization. The mol% or less, more preferably 20 mol% or more and 40 mol% or less. By adjusting the charged molar ratio of the monomer within this range, a sufficient crosslinked structure is formed inside the insulating layer, the content of polar groups is kept at a low level, and polarization of the insulating layer is suppressed.

The charged molar ratio of the polymerizable monomer containing the first functional group is 5% by mole or more and 50% by mole or less, preferably 10% by mole or more and 40% by mole or less, more preferably among all the monomers involved in the polymerization. Is 15 mol% or more and 30 mol% or less. By adjusting the charged molar ratio of the monomer within this range, a sufficient crosslinked structure is formed inside the insulating layer, the content of polar groups is kept at a low level, and polarization of the insulating layer is suppressed.

The polymer compound (A) has a polystyrene-equivalent weight average molecular weight of preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be linear, branched or cyclic.

Examples of the polymer compound (A) include poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co- [2- [O- (1′- Methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co- [2- [1'- (3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3', 4'-dimethylmaleimide)]-co-acrylonitrile- Co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacrylic) Royloxypropyl-3 ', 4'-dimethylmaleimide)]-co-acrylonitrile-co- [2- [1'-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene -Co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl- Methacrylate] -co-allyltrimethylgermanium), poly (styrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co-acrylonitrile-co- [ 2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyl trimer Lugermanium), poly ([N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [O- (1′-methylpropylideneamino) Carboxyamino] ethyl-methacrylate]), poly ([N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [1 ′-(3 ′ , 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co -[2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloylio) Cypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]) and the like .

<Polymer compound (B)>
Another preferable aspect of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention is a polymer compound having a plurality of photodimerization reactive groups, a fluorine atom, and a plurality of the first functional groups. It is. Among the polymer compounds, a polymer compound having a repeating unit represented by Formula (1), a repeating unit represented by Formula (2), and a repeating unit containing a first functional group. Such a polymer compound is referred to as a polymer compound (B).

When fluorine is introduced into the organic thin film transistor insulating layer material, the insulating layer formed from the material has low polarity, and polarization of the insulating layer is suppressed. In addition, when a cross-linked structure is formed inside the insulating layer, the movement of the molecular structure is suppressed, and the polarization of the insulating layer is suppressed. When the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the hysteresis of the organic thin film transistor is lowered and the operation accuracy is improved.

It is preferable that the fluorine atom does not replace the hydrogen atom of the main chain of the polymer compound, but replaces the hydrogen atom of the side chain or side group (pendant group). When the fluorine atom is substituted with a side chain or a side group, the affinity for other organic materials such as an organic semiconductor is not lowered, and in the formation of a layer containing the organic material, the organic material is exposed to the exposed surface of the insulating layer. It becomes easy to form a layer in contact.

For example, a polymer compound having a repeating unit having a group containing a fluorine atom, a repeating unit having a photodimerization reactive group, and a repeating unit having the first functional group corresponds to the polymer compound (B). .

Preferred examples of the group containing a fluorine atom include an aryl group in which a hydrogen atom is substituted with fluorine, an alkylaryl group in which a hydrogen atom is substituted with fluorine, particularly a phenyl group in which a hydrogen atom is substituted with fluorine, and a hydrogen atom in fluorine. A substituted alkylphenyl group;

Preferred examples of the photodimerization reactive group include the same groups as described above.

The repeating unit having a group containing a fluorine atom is preferably a repeating unit represented by the above formula (2).

In formula (2), R ₁ represents a hydrogen atom or a methyl group. In one certain form, R < ₁ > is a hydrogen atom.

In the formula (2), Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. In one certain form, Rf is a fluorine atom.
b represents an integer of 1 to 5. In one certain form, b is 5.

When Rf is an organic group having 1 to 20 carbon atoms having a fluorine atom, the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom may be a trifluoromethyl group or 2,2,2-trifluoroethyl. Group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, pentafluorophenyl group, trifluoromethylphenyl group and the like.

In the formula (2), R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

When R is a monovalent organic group having 1 to 20 carbon atoms, the monovalent organic group does not have a fluorine atom. Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R include groups having no fluorine atom among the specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _3. It is done.

In formula (2), R _aa represents a linking moiety that links the main chain and the side chain and may have a fluorine atom. The connecting portion may be a divalent group having a structure that does not exhibit reactivity under environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention. Specific examples of the linking moiety include a bond composed of a divalent organic group having 1 to 20 carbon atoms, an ether bond (—O—), a ketone bond (—CO—), an ester bond (—COO—, —OCO—). Amide bond (—NHCO—, —CONH—), urethane bond (—NHCOO—, —OCONH—), and a combination of these bonds. u represents an integer of 0 or 1. In one certain form, a is 1.

Examples of the divalent organic group having 1 to 20 carbon atoms include the same groups as the specific examples of the divalent organic group having 1 to 20 carbon atoms represented by R _bb .

The polymer compound (B) includes, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (1), a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (2), It can be produced by a method in which a polymerizable monomer containing a first functional group is copolymerized using a photopolymerization initiator or a thermal polymerization initiator.

Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the above formula (2) include 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, 2,3,4, Examples include 5,6-pentafluorostyrene and 4-fluorostyrene.

The polymer compound (B) that can be used in the present invention is a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (1), and a polymerization that is a raw material of the repeating unit represented by the above formula (2). A polymerizable monomer other than the polymerizable monomer and the polymerizable monomer containing the first functional group may be added during polymerization.

The amount of the polymerizable monomer used as the raw material of the repeating unit represented by the above formula (2) is adjusted so that the amount of fluorine atoms introduced into the polymer compound (B) becomes an appropriate amount.

The amount of fluorine atoms introduced into the polymer compound (B) is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and further preferably 10 to 10% by mass with respect to the mass of the polymer compound (B). 60% by mass. When the amount of the fluorine base paper is less than 1% by mass, the effect of reducing the hysteresis of the field effect organic thin film transistor may be insufficient. When the amount exceeds 80% by mass, the affinity with the organic semiconductor material is deteriorated and activated. It may be difficult to stack a layer thereon.

From the viewpoint of reducing the absolute value of the threshold voltage of the organic thin film transistor using the polymer compound (B), the polymer compound (B) has the number of repeating units that the polymer compound (B) has 100. The amount of the repeating unit represented by the formula (2) is preferably 30 to 80.

The polymer compound (B) has a polystyrene-equivalent weight average molecular weight of preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be linear, branched or cyclic.

Examples of the polymer compound (B) include poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co-pentafluorostyrene-co- [2- [ O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co-penta Fluorostyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4'-dimethylmaleimide)]-co-pentafluorostyrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino ] -Ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-pentafluorostyrene-co-acrylonitrile-co- [2- [ 1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co -Pentafluorostyrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium),
Poly (styrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co-pentafluorostyrene-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly ([N- (3-methacryloyloxypropyl-1'-cyclohexene-1 ', 2'- Dicarboximide)]-co-pentafluorostyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ([N- (3-methacryloyloxypropyl- 1′-cyclohexene-1 ′, 2′-dicarboximide)]-co-pentafluorostyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpi Zolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- (4-trifluoromethylstyrene) -co- [N- (3-methacryloyloxypropyl-1'-cyclohexene-1 ', 2'-di Carboximide)]-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- (4-trifluoromethylstyrene) -co- [N -(3-Methacryloyloxypropyl-1'-cyclohexene-1 ', 2'-dicarboximide)]-co- [2- [1'-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate ]) And the like.

<Polymer compound (C)>
Another preferred embodiment of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention has a plurality of photodimerization reactive groups, a plurality of the first functional groups, and two active hydrogens. It is a high molecular compound contained above. Such a polymer compound is referred to as a polymer compound (C). The active hydrogen may be directly bonded to the main chain constituting the polymer compound or may be bonded through a predetermined group. Moreover, active hydrogen may be contained in each structural unit which comprises a high molecular compound, and may be contained only in a part of structural unit. Furthermore, the active hydrogen may be bonded only to the terminal of the polymer compound.

Specific examples of the polymer compound (C) include two structural units each having a repeating unit represented by the formula (1) and a repeating unit containing a first functional group and one active hydrogen. Examples thereof include a high molecular compound having the above, a high molecular compound having a repeating unit represented by the formula (1) and a repeating unit containing a first functional group and having a structural unit having two or more active hydrogens. .

The polymer compound (C) includes, for example, a monomer having an active hydrogen-containing group and a monomer having an unsaturated bond such as a double bond, a polymerizable monomer that is a raw material for the repeating unit represented by the above formula (1), It can be produced by copolymerizing with a polymerizable monomer containing one functional group. In addition, a monomer having an active hydrogen-containing group and a double bond or other unsaturated bond, a polymerizable monomer serving as a raw material of the repeating unit represented by the above formula (1), and a polymerizable containing the first functional group A polymerizable monomer other than the monomer may be added during the polymerization. In the polymerization, a photopolymerization initiator or a thermal polymerization initiator may be applied. In addition, the thing similar to what was mentioned above is applicable as a polymerizable monomer, a photoinitiator, and a thermal polymerization initiator.

Examples of the monomer having an active hydrogen-containing group and an unsaturated bond include aminostyrene, hydroxystyrene, vinyl benzyl alcohol, aminoethyl methacrylate, ethylene glycol monovinyl ether, and 4-hydroxybutyl acrylate.

The polymer compound (C) has a polystyrene-equivalent weight average molecular weight of preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be linear, branched or cyclic.

The molar ratio of the polymerizable monomer containing the first functional group used in producing the polymer compound (C) to the monomer containing active hydrogen and the monomer having an unsaturated bond is preferably 60/100 to 150. / 100, more preferably 70/100 to 120/100, and still more preferably 90/100 to 110/100. If the molar ratio is less than 60/100, the active hydrogen may be excessive and the effect of reducing hysteresis may be reduced. If the molar ratio exceeds 150/100, the functional group that reacts with the active hydrogen will be excessive and the threshold voltage will be absolute. The value can be large.

Examples of the polymer compound (C) include poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co-aminostyrene-co- [2- [O -(1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-aminostyrene -Co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ', 4' -Dimethylmaleimide)]-co-aminostyrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl -Methacrylate]), poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-aminostyrene-co-acrylonitrile-co- [2- [O- ( 1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (styrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′- Dicarboximide)]-co-aminostyrene-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly ([N- (3-Methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboxyl )]-Co-aminostyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ([N- (3-methacryloyloxypropyl-1′- Cyclohexene-1 ′, 2′-dicarboximide)]-co-aminostyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (amino Styrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [O- (1′-methylpropylideneamino) carboxyamino ] Ethyl-methacrylate]), poly (aminostyrene-co- [N- (3-methacryloyloxypropyl-1'-cyclohexene-1 ', 2'-dicarboxymi) )]-Co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]) and the like.

<Polymer compound (D)>
Another preferred embodiment of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention has a plurality of photodimerization reactive groups, a fluorine atom, a plurality of the first functional groups, and A polymer compound containing two or more repeating units containing active hydrogen. Such a polymer compound is referred to as a polymer compound (D). The active hydrogen may be directly bonded to the main chain constituting the polymer compound or may be bonded via a predetermined group. Moreover, active hydrogen may be contained in each structural unit which comprises a high molecular compound, and may be contained only in a part of structural unit. Furthermore, the active hydrogen may be bonded only to the terminal of the polymer compound.

Specific examples of the polymer compound (D) include a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a repeating unit containing a first functional group. A polymer compound having two or more structural units having one active hydrogen, a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a first functional group And a polymer compound having a repeating unit and a structural unit having two or more active hydrogens.

The polymer compound (D) includes, for example, a monomer having an active hydrogen-containing group and a monomer having an unsaturated bond such as a double bond, a polymerizable monomer serving as a raw material for the repeating unit represented by the above formula (1), It can manufacture by copolymerizing with the polymerizable monomer used as the raw material of the repeating unit represented by Formula (2), and the polymerizable monomer containing a 1st functional group. In addition, the monomer which has unsaturated bonds, such as a group containing active hydrogen and a double bond, the polymerizable monomer used as the raw material of the repeating unit represented by the said Formula (1), the repetition represented by the said Formula (2) A polymerizable monomer other than the polymerizable monomer serving as the raw material of the unit and the polymerizable monomer containing the first functional group may be added during the polymerization. In the polymerization, a photopolymerization initiator or a thermal polymerization initiator may be applied. In addition, the thing similar to what was mentioned above is applicable as a polymerizable monomer, a photoinitiator, and a thermal polymerization initiator.

Specific examples of the monomer having an active hydrogen-containing group and an unsaturated bond include the monomers described above.

The polymer compound (D) has a polystyrene-equivalent weight average molecular weight of preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be linear, branched or cyclic.

The molar ratio of the polymerizable monomer, which is a raw material for the first functional group used in the production of the polymer compound (D), to the active hydrogen-containing group and the monomer having an unsaturated bond is preferably 60/100 to 150/100, more preferably 70/100 to 120/100, and still more preferably 90/100 to 110/100. If the molar ratio is less than 60/100, the active hydrogen may be excessive and the effect of reducing hysteresis may be reduced. If the molar ratio exceeds 150/100, the functional group that reacts with the active hydrogen will be excessive and the threshold voltage will be reduced. The absolute value may be large.

Examples of the polymer compound (D) include poly (styrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4′-dimethylmaleimide)]-co-aminostyrene-co-pentafluorostyrene-co. -[2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorostyrene-co- [N- (3-methacryloyloxypropyl-3 ′, 4'-dimethylmaleimide)]-co-aminostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co-pentafluorostyrene -Co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-aminostyrene-co-acrylic Ronitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorostyrene-co- [N- (3-methacryloyloxypropyl- 3 ′, 4′-dimethylmaleimide)]-co-aminostyrene-co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ( Styrene-co-pentafluorostyrene-co- [N- (3-methacryloyloxypropyl-3 ', 4'-dimethylmaleimide)]-co-aminostyrene-co-acrylonitrile-co- [2- [O- (1 '-Methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly Tylene-co-pentafluorostyrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co-aminostyrene-co-acrylonitrile-co- [2 -[1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly ([N- (3-methacryloyloxypropyl-1'-cyclohexene-1 ', 2′-dicarboximide)]-co-aminostyrene-co-pentafluorostyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ([N — (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co-aminostyrene -Co-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (aminostyrene-co-pentafluorostyrene-co- [ N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] ), Poly (aminostyrene-co-pentafluorostyrene-co- [N- (3-methacryloyloxypropyl-1′-cyclohexene-1 ′, 2′-dicarboximide)]-co- [2- [1 ′ -(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]) and the like.

<Active hydrogen compound (E)>
The organic thin film transistor insulating layer material of the present invention may contain an active hydrogen compound (E). The active hydrogen compound (E) reacts with the second functional group generated in the polymer compounds (A) to (D) and binds to it, thereby forming a crosslinked structure inside the insulating layer. it can. The active hydrogen compound (E) includes a low molecular compound containing two or more active hydrogens (hereinafter referred to as a low molecular active hydrogen compound (E-1)) and a polymer compound containing two or more active hydrogens ( Hereinafter, the polymer active hydrogen compound (E-2)) is included.

Examples of the active hydrogen typically include a hydrogen atom contained in an amino group, a hydroxy group, or a mercapto group. As active hydrogen, hydrogen contained in a phenolic hydroxy group, hydrogen contained in an alcoholic hydroxy group, aromatic amino group capable of favorably producing a reaction with the above-described reactive functional groups, in particular, isocyanato groups and isothiocyanato groups. Hydrogen contained in is preferred.

Specific examples of the low molecular active hydrogen compound (E-1) include a compound having a structure in which two or more active hydrogen-containing groups are bonded to a low molecular structure. Examples of this low molecular structure include an alkyl structure and a benzene ring structure. Specific examples of the low molecular weight compound include amine compounds, alcohol compounds, phenol compounds, and thiol compounds. In the present specification, the “alkyl structure” means a linear, branched, or cyclic structure composed of an aliphatic hydrocarbon. On the other hand, the “benzene ring structure” means a linear, branched, or cyclic structure composed of an aromatic hydrocarbon.

Examples of amine compounds include ethylenediamine, propylenediamine, hexamethylenediamine, N, N, N ′, N ′,-tetraaminoethylethylenediamine, ortho-phenylenediamine, meta-phenylenediamine, para-phenylenediamine, N, N′-diphenyl-para-phenylenediamine, melamine, 2,4,6-triaminopyrimidine, 1,5,9-triazacyclododecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1 , 4-bis (3-aminopropyldimethylsilyl) benzene, 3- (2-aminoethylaminopropyl) tris (trimethylsiloxy) silane.

Examples of alcohol compounds include ethylene glycol, 1,2-dihydroxypropane, glycerol, and 1,4-dimethanolbenzene.

Examples of phenolic compounds include 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene (hydroquinone), 1,2-dihydroxynaphthalene, resorcin, fluoroglycerol, 2,3,4- Examples include trihydroxybenzaldehyde and 3,4,5-trihydroxybenzamide.

Examples of thiol compounds include ethylene dithiol and para-phenylene dithiol.

As the low molecular weight compound containing two or more active hydrogens, alcohol compounds, phenol compounds, and aromatic amine compounds are preferable.

On the other hand, in the polymer active hydrogen compound (E-2), the active hydrogen may be directly bonded to the main chain constituting the polymer compound or may be bonded through a predetermined group. The active hydrogen may be contained in the structural unit constituting the polymer compound. In that case, it may be contained in each structural unit, or may be contained only in a part of the structural units. . Furthermore, the active hydrogen may be bonded only to the terminal of the polymer compound.

Specific examples of the polymer active hydrogen compound (E-2) include a compound having a structure in which a group containing two or more active hydrogens is bonded to a polymer structure.

The polymer active hydrogen compound (E-2) is obtained by polymerizing a monomer having an active hydrogen-containing group and an unsaturated bond such as a double bond alone or by repeating the monomer represented by the above formula (1). Copolymerizing with a polymerizable monomer that is a raw material of the repeating unit represented by the above formula (2) or the repeating unit containing the first functional group, or by copolymerizing the monomer with another copolymerizable compound. It is obtained by forming a coalescence. The polymerization or copolymerization of these polymerizable monomers may be performed using a method usually used by those skilled in the art.

In the polymerization, a photopolymerization initiator or a thermal polymerization initiator may be applied. In addition, the thing similar to what was mentioned above is applicable as a polymerizable monomer, a photoinitiator, and a thermal polymerization initiator.

Among the monomers containing active hydrogen and monomers having unsaturated bonds, monomers containing amino groups are preferred.

Also, as a polymer compound containing two or more active hydrogens, a novolak resin obtained by condensing a phenol compound and formaldehyde in the presence of an acid catalyst is also preferably used.

The weight average molecular weight in terms of polystyrene of the polymer compound containing two or more groups containing active hydrogen is preferably from 1,000 to 1,000,000, and more preferably from 3,000 to 500,000. Thereby, the effect that the flatness and uniformity of the insulating layer are improved can be obtained. The weight average molecular weight in terms of polystyrene is measured by GPC.

<Organic thin film transistor insulating layer material>
The polymer compounds (A) to (D) are all light and heat energy crosslinkable and can be used as the organic thin film transistor insulating layer material of the present invention. The polymer compounds (A) and (B) do not have active hydrogen. However, when the heating is performed in an atmosphere containing moisture such as in the air, the second functional group can react with water, and the polymer compounds (A) and (B) can also be thermally crosslinked. One preferable aspect of the organic thin film transistor insulating layer material of the present invention is a composition containing the polymer compound (A) and / or (B) and the active hydrogen compound (E). Among the compositions, a composition containing the polymer compound (B) and the active hydrogen compound (E) is more preferable.

The mixing ratio of the polymer compound (A) and / or (B) and the active hydrogen compound (E) is determined by the second functional group that can be generated from the polymer compound (A) and / or (B) and the active hydrogen. A ratio in which the molar ratio of the group containing active hydrogen in the compound (E) is 60/100 to 150/100 is preferable. The ratio is more preferably 70/100 to 120/100, and still more preferably 90/100 to 110/100. If the molar ratio is less than 60/100, the active hydrogen may be excessive and the effect of reducing hysteresis may be reduced. If the molar ratio exceeds 150/100, the functional group that reacts with the active hydrogen is excessive. The absolute value of the threshold voltage may increase.

Another preferred embodiment of the organic thin film transistor insulating layer material of the present invention is a polymer compound (C). Among the polymer compounds (C), the polymer compound (D) is more preferable. Since the polymer compound (C) and the polymer compound (D) have the first functional group and the group containing active hydrogen, they can be used alone for the organic thin film transistor insulating layer material of the present invention. .

The organic thin film transistor insulating layer material of the present invention contains an organic group and a functional group bonded to the polymer compounds (A) to (E). The contents of the organic group and the functional group are appropriately determined by adjusting the amount of the repeating unit having the organic group and the functional group in consideration of the performance required for the organic thin film transistor insulating layer material.

In a preferred embodiment, the molar fraction of the repeating unit containing a photodimerization reactive group is 0.01 to based on the total number of repeating units of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention. It is 0.7, preferably 0.05 to 0.6, more preferably 0.1 to 0.5. If the molar fraction of the repeating unit containing the photodimerization reactive group is less than 0.01, curing may be insufficient, and if it exceeds 0.7, the transistor characteristics may be adversely affected.

The molar fraction of the repeating unit containing the first functional group is 0.01 to 0.7, preferably 0.05 to 0.6, more preferably 0.1 to 0.5. If the molar fraction of the repeating unit containing the first functional group is less than 0.01, curing may be insufficient, and if it exceeds 0.7, transistor characteristics may be adversely affected. The amount of active hydrogen is determined based on the amount that reacts with the first functional group without excess or deficiency.

The amount of fluorine introduced into the polymer compound is preferably 50% by mass or less, preferably 1 to 40% by mass, more preferably 5 to 35% by mass with respect to the total amount of the polymer compound. When the amount of fluorine exceeds 50% by mass, the affinity with the organic semiconductor material is deteriorated, and it may be difficult to stack the layer thereon.

The organic thin film transistor insulating layer material of the present invention includes a solvent for mixing and viscosity adjustment, a crosslinking agent used for crosslinking the polymer compounds (A) to (D), and an additive used in combination with the crosslinking agent. Etc. may be included. Solvents used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic carbonization such as xylene. Examples thereof include a hydrogen solvent, a ketone solvent such as acetone, an acetate solvent such as butyl acetate, an alcohol solvent such as isopropyl alcohol, a halogen solvent such as chloroform, and a mixed solvent of these solvents. Moreover, as an additive, the catalyst for promoting a crosslinking reaction, a leveling agent, a viscosity modifier, etc. can be used.

The organic thin film transistor insulating layer material of the present invention is a composition used for forming an insulating layer contained in an organic thin film transistor. Among the insulating layers of organic thin film transistors, it is preferably used for forming an overcoat layer or a gate insulating layer. The organic thin film transistor insulating layer material is preferably an organic thin film transistor overcoat layer composition or an organic thin film transistor gate insulating layer composition, and more preferably an organic thin film transistor gate insulating layer material.

<Organic thin film transistor>
FIG. 1 is a schematic cross-sectional view showing the structure of a bottom gate top contact organic thin film transistor according to an embodiment of the present invention. The organic thin film transistor includes a substrate 1, a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, an organic semiconductor layer 4 formed on the gate insulating layer 3, A source electrode 5 and a drain electrode 6 formed on the organic semiconductor layer 4 with a channel portion interposed therebetween, and an overcoat 7 covering the entire element are provided.

A bottom gate top contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, an organic semiconductor layer formed on the gate insulating layer, and a source electrode formed on the organic semiconductor layer. It can be manufactured by forming a drain electrode and forming an overcoat. The organic thin film transistor insulating layer material of the present invention is suitably used for forming a gate insulating layer as an organic thin film transistor gate insulating layer material. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat layer material.

FIG. 2 is a schematic cross-sectional view showing the structure of a bottom gate bottom contact type organic thin film transistor which is an embodiment of the present invention. In this organic thin film transistor, a substrate 1, a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, and a channel portion on the gate insulating layer 3 are formed. A source electrode 5 and a drain electrode 6, an organic semiconductor layer 4 formed on the source electrode 5 and the drain electrode 6, and an overcoat 7 that covers the entire element are provided.

A bottom gate bottom contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, a source electrode and a drain electrode formed on the gate insulating layer, and a source electrode and a drain electrode. It can be manufactured by forming an organic semiconductor layer thereon and forming an overcoat. The organic thin film transistor insulating layer material of the present invention is suitably used for forming a gate insulating layer as an organic thin film transistor gate insulating layer material. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat layer material.

For the formation of the gate insulating layer or overcoat layer, if necessary for the organic thin film transistor insulating layer material, a solvent or the like is added to prepare an insulating layer coating solution, and the insulating layer coating solution is placed under the gate insulating layer or overcoat layer. It is performed by applying to the surface of the layer located, drying and curing. The organic solvent used in the insulating layer coating solution is not particularly limited as long as it dissolves the organic thin film transistor insulating layer material, but is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. at normal pressure. . Examples of the organic solvent include 2-heptanone (boiling point 151 ° C.) and propylene glycol monomethyl ether acetate (boiling point 146 ° C.). A leveling agent, a surfactant, a curing catalyst, and the like can be added to the insulating layer coating solution as necessary. The organic thin film transistor insulating layer material of the present invention can also be used for forming a gate insulating layer as an organic thin film transistor gate insulating layer composition.

The insulating layer coating solution can be applied onto the gate electrode by a known method such as spin coating, die coater, screen printing, or ink jet. The formed coating layer is dried as necessary. Drying here means removing the solvent contained in the applied resin composition.

The dried coating layer is then cured. Curing means that the organic thin film transistor insulating layer material is crosslinked. Cross-linking of the transistor insulating layer material is performed, for example, by applying electromagnetic wave irradiation or heat to the coating layer. Then, a second functional group is generated from the first functional group of the polymer compound (A) or (B), and the second functional group reacts with the active hydrogen-containing group of the active hydrogen compound (E). Because. Alternatively, the second functional group is generated from the first functional group of the polymer compound (C) or (D), and the second functional group reacts with the active hydrogen-containing group in the molecule.

Crosslinking of the organic thin film transistor insulating layer material is also performed by irradiating the coating layer with electromagnetic waves or electron beams. This is because when the coating layer is irradiated with an electromagnetic wave or an electron beam, dimerization occurs due to the cyclization reaction of the photodimerization reactive groups of the polymer compounds (A) to (D).

When the first functional group contained in the polymer compounds (A) to (D) is a functional group that generates a second functional group that reacts with active hydrogen upon irradiation with electromagnetic waves, the organic thin film transistor insulating layer is: Forming the coating layer on the substrate by applying a liquid containing an organic thin film transistor insulating layer material to the substrate; and irradiating the coating layer with an electromagnetic wave or an electron beam. Is preferred.

When the first functional group contained in the polymer compounds (A) to (D) is a functional group that generates a second functional group that reacts with active hydrogen by the action of heat, an organic thin film transistor insulating layer material is formed. Preferably, it is formed by a forming method including a step of coating a liquid containing the substrate on the substrate and forming a coating layer on the substrate; and a step of irradiating the coating layer with an electromagnetic wave or an electron beam. The layer includes a step of applying a liquid containing an organic thin film transistor insulating layer material to a substrate to form a coating layer on the substrate; a step of irradiating the coating layer with an electromagnetic wave or an electron beam; and heating the coating layer. It is more preferable to form by the forming method including the step of applying.

This is because the crosslink density of the insulating layer is improved by performing both the step of irradiating the coating layer with electromagnetic waves or electron beams and the step of applying heat to the coating layer. In particular, when the organic thin film transistor insulating layer material is used for the gate insulating layer, the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor are reduced. It is considered that the polarization at the time of voltage application is further suppressed by improving the crosslinking density of the insulating layer, and the absolute value and hysteresis of the threshold voltage of the organic thin film transistor are reduced.

When heat is applied to the coating layer, the coating layer is heated to a temperature of about 80 to 250 ° C., preferably about 100 to 230 ° C., and maintained for about 5 to 120 minutes, preferably about 10 to 60 minutes. If the heating temperature is too low or the heating time is too short, the insulating layer is not sufficiently crosslinked, and if the heating temperature is too high or the heating time is too long, the insulating layer may be damaged.

When irradiating the coating layer with electromagnetic waves, the irradiation conditions are adjusted in consideration of the degree of crosslinking and damage of the insulating layer. In the case of heating by applying a microwave, the application condition is adjusted in consideration of the cross-linking of the insulating layer and the degree of damage.

The wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 150 to 410 nm. When the wavelength of the electromagnetic wave to be irradiated exceeds 450 nm, the organic thin film transistor insulating layer material may be insufficiently crosslinked. As electromagnetic waves, ultraviolet rays are preferable.

Irradiation with ultraviolet rays can be performed using, for example, an exposure apparatus used for manufacturing a semiconductor or a UV lamp used for curing a UV curable resin. The electron beam irradiation can be performed using, for example, a micro electron beam irradiation tube. Heating can be performed using a heater, an oven, or the like. Other irradiation conditions and heating conditions are appropriately determined according to the type and amount of the photodimerization reactive group.

A self-assembled monolayer may be formed on the gate insulating layer. The self-assembled monolayer can be formed, for example, by treating the gate insulating layer with a solution obtained by dissolving 1 to 10% by weight of an alkylchlorosilane compound or an alkylalkoxysilane compound in an organic solvent.

Examples of the alkylchlorosilane compound include methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, decyltrichlorosilane, and octadecyltrichlorosilane.

Examples of the alkylalkoxysilane compound include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, and octadecyltrimethoxysilane.

The substrate 1, gate electrode 2, source electrode 5, drain electrode 6 and organic semiconductor layer 4 may be composed of commonly used materials and methods. Resin or plastic plates, films, glass plates, silicon plates, etc. are used as the material of the substrate. As the electrode material, chromium, gold, silver, aluminum, molybdenum, or the like is used, and the electrode is formed by a known method such as a vapor deposition method, a sputtering method, a printing method, or an ink jet method.

As the organic semiconductor compound for forming the organic semiconductor layer 4, a π-conjugated polymer is used. For example, polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles, poly (P -Phenylene vinylene) and the like can be used. In addition, low-molecular substances having solubility in organic solvents, for example, polycyclic aromatic derivatives such as pentacene, phthalocyanine derivatives, perylene derivatives, tetrathiafulvalene derivatives, tetracyanoquinodimethane derivatives, fullerenes, carbon nanotubes Etc. can be used. Specifically, 2,1,3-benzothiadiazole-4,7-di (ethylene boronate) and 2,6-dibromo- (4,4-bis-hexadecanyl-4H-cyclopenta [2,1-b Condensate with 3,4-b ′]-dithiophene, 9,9-di-n-octylfluorene-2,7-di (ethylene boronate) and 5,5′-dibromo-2,2′-; Examples thereof include condensates with bithiophene.

The organic semiconductor layer can be formed, for example, by adding a solvent or the like if necessary for the organic semiconductor compound, preparing an organic semiconductor coating solution, applying the organic semiconductor coating solution on the gate insulating layer, and applying the organic semiconductor coating solution to the organic semiconductor coating solution. This is done by drying. In the present invention, the resin constituting the gate insulating layer has a benzene ring and has an affinity for an organic semiconductor compound. Therefore, a uniform and flat interface is formed between the organic semiconductor layer and the gate insulating layer by the coating and drying method.

The solvent used in the organic semiconductor coating solution is not particularly limited as long as it dissolves or disperses the organic semiconductor, but is preferably a solvent having a boiling point of 50 ° C. to 200 ° C. at normal pressure. Examples of the solvent include chloroform, toluene, anisole, 2-heptanone, and propylene glycol monomethyl ether acetate. The organic semiconductor coating liquid can be applied onto the gate insulating layer by a known method such as spin coating, die coater, screen printing, and ink jet as in the case of the insulating layer coating liquid.

The organic thin film transistor of the present invention may be coated with an overcoat material for the purpose of protecting the organic thin film transistor and improving the smoothness of the surface.

The insulating layer manufactured using the organic thin film transistor insulating layer material of the present invention can be laminated with a flat film or the like, and a laminated structure can be easily formed. Moreover, an organic electroluminescent element can be suitably mounted on the insulating layer.

A display member having an organic thin film transistor can be suitably produced using the organic thin film transistor insulating layer material of the present invention. A display provided with a display member can be manufactured using the display member having the organic thin film transistor.

The organic thin film transistor insulating layer material of the present invention can also be used for forming a layer included in a transistor other than an insulating layer and a layer included in an organic electroluminescence element.

Hereinafter, the present invention will be described with reference to examples, but it goes without saying that the present invention is not limited to the examples.

Synthesis example 1
(Synthesis of Compound 1)
In a 500 ml eggplant flask containing a water trap and stirrer, 25 g of 1-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry), 12 g of 3-aminopropanol, and 200 ml of toluene are placed in an oil bath. The reaction was carried out at 140 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated with a rotary evaporator, and 100 ml of diethyl ether (manufactured by Wako Pure Chemical Industries) was added. The obtained diethyl ether solution was transferred to a separatory funnel, washed with an aqueous sodium carbonate solution, and then washed with water until the aqueous layer became neutral and separated. After the organic layer was dried over anhydrous magnesium sulfate, the solid was filtered off and the filtrate was concentrated with a rotary evaporator to obtain Compound 1 as a tan viscous liquid.

Compound 1

(Synthesis of Compound 2)
In a 1 L three-necked flask equipped with a three-way cock, 26.18 g of Compound 1, 11.31 g of methacrylic acid, 27.10 g of N, N′-dicyclohexylcarbodiimide (manufactured by Wako Pure Chemical Industries), 4-dimethylaminopyridine (Japanese) 400 ml of 1,4-dioxane was added and the reaction was allowed to stir for 24 hours under a nitrogen atmosphere.

After completion of the reaction, the precipitate was filtered off, the filtrate was concentrated with a rotary evaporator, and 100 ml of diethyl ether (manufactured by Wako Pure Chemical Industries) was added. The obtained diethyl ether solution was transferred to a separatory funnel, washed with an aqueous sodium carbonate solution, and then washed with water until the aqueous layer became neutral and separated.
After the organic layer was dried over anhydrous magnesium sulfate, the solid was filtered off and the filtrate was concentrated with a rotary evaporator to obtain Compound 2 as a tan viscous liquid.

Compound 2

(Synthesis of polymer compound 3)
In a 50 ml pressure vessel (Ace), 2.00 g of 2,3,4,5,6-pentafluorostyrene (Aldrich), 0.82 g of aminostyrene (Tokyo Kasei), 2- (O- [1 1.65 g of '-methylpropylideneamino] carboxyamino) ethyl-methacrylate (manufactured by Showa Denko, trade name “Karenz MOI-BM”), 2.86 g of

compound

2, 2,2′-azobis (2-methylpro 0.04 g of (pionitrile) and 17.17 g of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and after argon gas was bubbled, it was sealed. Polymerization was performed in an oil bath at 60 ° C. for 20 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 3 was dissolved. The high molecular compound 3 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

Polymer compound 3

The weight average molecular weight obtained from the standard polystyrene of the obtained polymer compound 3 was 50,000 (GPC manufactured by Shimadzu, one Tskel super HM-H + one Tskel super H2000, mobile phase = THF).

Synthesis example 2
(Synthesis of polymer compound 4)
1.88 g of 2,1,3-benzothiadiazole-4,7-di (ethylene boronate) and 2,6-dibromo- (4,4-bis-hexadecanyl-4H-cyclopenta [2,1-b; In toluene (80 mL) containing 3.81 g of 3,4-b ′]-dithiophene, under nitrogen, 0.75 g of tetrakis (triphenylphosphine) palladium, methyltrioctylammonium chloride (manufactured by Aldrich, trade name “Aliquat”) 336 "(R)) and 24 mL of 2M aqueous sodium carbonate solution were added. The mixture was stirred vigorously and heated to reflux for 24 hours. The viscous reaction mixture was poured into 500 mL of acetone and mixed with A yellow polymer was precipitated which was collected by filtration, washed with acetone and vacuum oven And dried overnight at Oite 60 ° C.. The resulting polymer is called polymer compound 4. Polymer Compound 4, .n which has the following repeating unit represents the number of repeating units.

Polymer compound 4

The weight average molecular weight obtained from the standard polystyrene of the polymer compound 4 was 32000 (GPC manufactured by Shimadzu, one Tskel super HM-H + one Tskel super H2000, mobile phase = THF).

Example 1
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
Into a 10 ml sample bottle, 2.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 3 obtained in Synthesis Example 1 and 2.00 g of propylene glycol monomethyl ether acetate are added and dissolved while stirring. A uniform coating solution 1 as a material was prepared.

The obtained coating solution was filtered using a membrane filter having a pore diameter of 0.2 μm, spin-coated on a glass substrate with a chromium electrode, and then dried on a hot plate at 100 ° C. for 1 minute. Then, after irradiating UV light (wavelength 365 nm) of 1600 mJ / cm ² using an aligner (manufactured by Canon; PLA-521), the gate insulating layer is obtained by baking at 200 ° C. for 30 minutes on a hot plate in nitrogen. It was.

Next, the polymer compound 4 was dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and this was filtered through a membrane filter to prepare a coating solution. .

The obtained coating solution is applied on the gate insulating layer by a spin coating method to form an active layer having a thickness of about 30 nm, and then, on the active layer by a vacuum deposition method using a metal mask, A field effect organic thin film transistor was manufactured by forming a source electrode and a drain electrode (having a laminated structure in the order of molybdenum oxide and gold from the active layer side) having a channel length of 20 μm and a channel width of 2 mm.

<Evaluation of transistor characteristics>
The field effect organic thin film transistor thus fabricated has the transistor characteristics of a vacuum probe (BCT22MDC-5-5) under the condition that the gate voltage Vg is changed to 20 to -40V and the source-drain voltage Vsd is changed to 0 to -40V. HT-SCU; Nagase Electronic Equipment
s Service Co., LTD). The results are shown in Table 1.

The hysteresis of the field effect organic thin film transistor is that the source-drain voltage Vsd is −40 V, and the threshold voltage Vth1 and the gate voltage Vg are changed from −40 V to 20 V when the gate voltage Vg is changed from 20 V to −40 V. It was expressed as a voltage difference from the threshold voltage Vth2.

Comparative Example 1
(Manufacture of field-effect organic thin-film transistors)
In a 10 ml sample bottle, 1.00 g of polyvinylphenol-co-polymethyl methacrylate (manufactured by Aldrich, Mn = 6700), N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine (Sumitomo Chemical) Product) 0.163 g, thermal acid generator (manufactured by Midori Chemical Co., Ltd., trade name: TAZ-108) 0.113 g, 2-heptanone 7.00 g, stirred and dissolved to obtain a uniform coating solution 2 Prepared.

A field effect organic thin film transistor was produced in the same manner as in Example 1 except that the coating solution 2 was used in place of the coating solution 1 and UV irradiation was not performed when forming the gate insulating layer. When the transistor characteristics were measured and evaluated, it did not operate as a transistor in the region where the gate voltage Vg was 20V to -40V.

1 ... substrate,
2 ... Gate electrode,
3 ... gate insulating layer,
4 ... Organic semiconductor layer,
5 ... Source electrode,
6 ... drain electrode,
7 ... Overcoat.

Claims

Formula (1)

[Wherein R 2 represents a hydrogen atom or a methyl group. R 3 and R 4 each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. The carbon atom in R 3 and the carbon atom in R 4 may be bonded to form a 5-membered ring or a 6-membered ring. R bb represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. c represents an integer of 0 or 1. ]
And a second functional group containing a first functional group, and the first functional group generates a second functional group that reacts with active hydrogen by the action of electromagnetic waves or heat. Organic thin-film transistor insulating-layer material containing the high molecular compound (A) which is a functional group to do.
The polymer compound (A) is further represented by the formula (2)

[Wherein, R 1 represents a hydrogen atom or a methyl group. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. R aa represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. u represents an integer of 0 or 1, and b represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of Rf, they may be the same or different. ]
The organic thin-film transistor insulating-layer material of Claim 1 which has a repeating unit represented by these.
3. The organic thin film transistor according to claim 1, wherein the first functional group is at least one group selected from the group consisting of an isocyanato group blocked with a blocking agent and an isothiocyanate group blocked with a blocking agent. Insulating layer material.
The isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula (3):

(3)
[Wherein, Xa represents an oxygen atom or a sulfur atom, and R 5 and R 6 are the same or different and represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The organic thin film transistor insulating layer material according to claim 3, which is a group represented by:
An isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent are represented by the formula (4):

(4)
[Wherein, Xb represents an oxygen atom or a sulfur atom, and R 7 to R 9 are the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The organic thin film transistor insulating layer material according to claim 3, which is a group represented by:
6. The polymer compound (A) according to any one of claims 1 to 5, further comprising two or more structural units having one active hydrogen or a structural unit having two or more active hydrogens. Organic thin film transistor insulating layer material.
Furthermore, it contains at least one active hydrogen compound selected from the group consisting of an active hydrogen compound which is a low molecular compound containing two or more active hydrogens and an active hydrogen compound which is a polymer compound containing two or more active hydrogens The organic thin film transistor insulating layer material according to any one of claims 1 to 6.
A step of applying a liquid containing the organic thin film transistor insulating layer material according to any one of claims 1 to 7 to a substrate to form a coating layer on the substrate; and electromagnetic waves or electron beams to the coating layer Irradiating;
A method for forming an organic thin film transistor insulating layer comprising:
Applying a liquid containing the organic thin film transistor insulating layer material according to any one of claims 1 to 7 to a substrate to form a coating layer on the substrate;
Irradiating the coating layer with electromagnetic waves or electron beams; and applying heat to the coating layer;
A method for forming an organic thin film transistor insulating layer comprising:
The method for forming an organic thin film transistor insulating layer according to claim 8 or 9, wherein the electromagnetic wave is ultraviolet light.
An organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material according to any one of claims 1 to 7.
The organic thin film transistor according to claim 11, wherein the organic thin film transistor insulating layer is a gate insulating layer.
A display member comprising the organic thin film transistor according to claim 11.
A display comprising the display member according to claim 13.