TWI488845B - Composition for insulation layer of organic thin film transistor and organic thin film transistor - Google Patents

Description

Organic thin film transistor insulating layer composition and organic thin film transistor

The present invention relates to a composition for an organic thin film transistor insulating layer which is suitable for forming an insulating layer provided in an organic thin film transistor, and more particularly to a composition for an organic thin film transistor insulating layer which is suitable for forming an overcoat insulating layer.

Since the organic thin film transistor can be manufactured at a lower temperature than the inorganic semiconductor, a plastic substrate or a thin film can be used as the substrate, and by using such a substrate, a flexible, lightweight, and easily damaged element can be obtained. Further, by forming a film by coating or printing using a solution containing an organic material, an element can be fabricated, and a plurality of elements can be fabricated on a large-area substrate at low cost.

Furthermore, since the types of materials that can be used for review of the crystal are very abundant, if materials having different molecular structures are used for review, it is possible to manufacture an element having a wide range of characteristic changes.

In one type of field effect type organic thin film transistor which is an organic thin film transistor, the voltage applied to the gate electrode acts on the semiconductor layer via the gate insulating layer, and the amount of current of the gate current is controlled. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer.

Further, the organic semiconductor compound used in the field effect type organic thin film transistor is susceptible to environmental influences such as humidity and oxygen, and the transistor characteristics are liable to cause deterioration over time due to humidity, oxygen, and the like.

Therefore, in the bottom gate type organic field effect transistor device structure in which the organic semiconductor compound is exposed, it is necessary to form a protective layer covering the entire device structure to protect the organic semiconductor compound from contact with the outside air. On the other hand, in the top gate type organic field effect transistor device structure, the organic semiconductor compound is covered by the gate insulating layer and protected.

As described above, in order to form a protective insulating layer or a gate insulating layer covering the organic semiconductor layer in the field effect type organic thin film transistor, a composition containing a polymer compound and a solvent is used. In the present specification, the insulating layer or the insulating film of the organic thin film transistor such as the protective insulating layer or the gate insulating layer is referred to as an organic thin film transistor insulating layer.

A material constituting the organic thin film transistor insulating layer (hereinafter referred to as an organic thin film transistor insulating layer material) is, for example, a copolymer containing tetrafluoroethylene (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Special Table 2005-513788

However, if oxygen or moisture in the atmosphere intrudes into the organic thin film transistor, it acts on the organic semiconductor compound, forms a trap of electric charge, and increases the absolute value of the threshold voltage. Therefore, an organic field effect transistor including an insulating layer formed using the above-described organic thin film transistor insulating layer material has a problem that the absolute value of the threshold voltage when driving in the atmosphere is large.

An object of the present invention is to provide a composition for an organic thin film transistor insulating layer which can produce an organic thin film transistor having a small absolute value of a critical voltage when driven in the atmosphere.

That is, the present invention provides a composition for an organic thin film transistor insulating layer comprising: a compound (A) having a group having a cyclic ether structure, and a fluorine-containing solvent (B).

In one aspect, the group having the cyclic ether structure is at least one group selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2):

[wherein, R ₁ to R ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the organic group may be substituted by a fluorine atom]

[wherein R ₄ to R ₈ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the organic group may be substituted by a fluorine atom].

In one aspect, the fluorine-containing solvent is an aromatic fluorine compound having 6 to 20 carbon atoms.

In one aspect, the composition for an organic thin film transistor insulating layer further comprises a fluororesin (C).

In one aspect, the fluororesin (C) is at least one fluororesin selected from the group consisting of a fluororesin (C-1) defined below and a fluororesin (C-2) defined below.

Fluororesin (C-1): a fluororesin containing a repeating unit represented by the formula (3) and a repeating unit represented by the formula (4);

[wherein, X represents a monovalent organic group having a fluorine atom of 1 to 20, a fluorine atom or a chlorine atom]

[wherein R ₉ represents an alkylene group. The hydrogen atom in the alkyl group can be substituted by a fluorine atom].

Fluororesin (C-2): a fluororesin containing a repeating unit represented by the formula (5) and containing two or more first functional groups, wherein the first functional group is caused by electromagnetic wave irradiation or heat The functional group of the second functional group that reacts with the active hydrogen is formed.

[wherein R ₁₀ to R ₁₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the organic group may be substituted by a fluorine atom. 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. Raa represents a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group may be substituted by a fluorine atom. a represents an integer of 0 to 20, and m represents an integer of 1 to 5. When Raa is plural, the numbers may be the same or different. When R is plural, the numbers may be the same or different. When Rf is plural, the numbers may be the same or different.

In one aspect, the first functional group is selected from the group consisting of isocyanato blocked by a blocking agent and isothiocyanato blocked by a blocking agent. At least 1 base.

In one aspect, the first functional group is a group represented by the formula (6):

[wherein, Xa represents an oxygen atom or a sulfur atom. R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms].

In one aspect, the first functional group is a group represented by the formula (7):

[wherein, Xb represents an oxygen atom or a sulfur atom. R ₁₅ , R ₁₆ and R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms].

Furthermore, the present invention provides an organic thin film transistor having a source electrode, a gate electrode, a gate electrode, an organic semiconductor layer, and an insulating layer formed using the composition for any of the organic thin film transistor insulating layers described above.

In one aspect, the insulating layer is a protective insulating layer.

Moreover, the present invention provides a member for a display comprising the aforementioned organic thin film transistor.

Moreover, the present invention provides a display including the above-described member for a display.

The organic thin film transistor produced by using the composition for an organic thin film transistor insulating layer of the present invention has a small absolute value of a critical voltage when driven in the atmosphere.

Next, the present invention will be described in more detail.

(Composition for organic thin film transistor insulating layer) <Compound (A)>

The compound (A) contained in the composition for an organic thin film transistor insulating layer of the present invention has a group having a cyclic ether structure. The term "cyclic ether structure" means a structure in which the carbon of the cyclic hydrocarbon is replaced by oxygen. The number of atoms forming a ring in the cyclic ether structure is preferably 10 or less, more preferably 6 or less. The number of oxygen forming a ring in the cyclic ether structure is preferably 2 or less, more preferably 1.

The group having a cyclic ether structure is subjected to ring-opening by a cationic polymerization initiator which forms a cation by heating or light irradiation, and undergoes an addition reaction with each other. As a result, the compound (A) is polymerized and polymerized to form a film exhibiting high tensile strength.

The group having a cyclic ether structure is preferably at least one group selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2). Among them, the group represented by the formula (2) is particularly preferable because it provides a film having excellent solvent resistance.

In the formulae (1) and (2), R ₁ to R ₈ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the organic group may be substituted by a fluorine atom.

The monovalent organic group having 1 to 20 carbon atoms may be any of a straight chain, a branched chain, and a cyclic group, and may be saturated or unsaturated.

The monovalent organic group having 1 to 20 carbon atoms may, for example, be a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 20 carbon atoms, or a carbon number of 6 to 20 The aromatic hydrocarbon group is preferably a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

In the linear hydrocarbon group having 1 to 20 carbon atoms, the branched hydrocarbon group having 3 to 20 carbon atoms, and the cyclic hydrocarbon group having 3 to 20 carbon atoms, the hydrogen atom contained in the group may be substituted by a fluorine atom.

The hydrogen atom in the aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted with an alkyl group, a halogen atom or the like.

A monovalent organic group having 1 to 20 carbon atoms which may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and a ring. Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cylcohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthracenyl, tolyl, di Xylyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butylphenyl, methyl Naphthyl, dimethylnaphthyl, trimethylnaphthyl, vinyl naphthyl, methyl fluorenyl, ethyl decyl, pentafluorophenyl, trifluoromethylphenyl, chlorophenyl, bromine Phenyl and the like.

The monovalent organic group having 1 to 20 carbon atoms is preferably an alkyl group.

The group having a cyclic ether structure may, for example, be a group having an epoxy structure or a group having an oxetane structure. In the group having an oxetane structure, a group having a 3-ethyloxetane structure is contained.

The compound (A) is a hydrogen atom or an organic group other than the group having a cyclic ether structure. The valence of the organic group is the number of groups having a cyclic ether structure contained in the compound (A). The organic group may, for example, be a monovalent organic group having 1 to 20 carbon atoms or a divalent organic group having 1 to 20 carbon atoms.

Specific examples of the compound (A) include bis(3'-glycidoxypropyl)-1,1,3,3-tetramethyldioxane and 3-ethyl-3-(2'). -ethylhexyloxymethyl)-oxetane, 3-ethyl-3-{[(3-ethyl-oxetan-3-yl)methoxy]methyl}oxa Cyclobutane.

<Fluorinated solvent (B)>

The fluorine-containing solvent (B) contained in the composition for an organic thin film transistor insulating layer of the present invention is such that the compound (A) in the composition is changed under the usual environmental conditions used in the production of the organic thin film transistor. An organic compound having a fluorine atom which is fluidized and volatilizable.

When the fluorine-containing solvent (B) is contained in the composition for an organic thin film transistor insulating layer, the composition for an organic thin film transistor insulating layer has a property of enhancing wettability and diffusion when used as a film. Therefore, a thin insulating layer can be formed by a coating method or a printing method, and the flatness of the surface of the formed insulating layer can be improved.

Further, the organic compound having a fluorine atom lacks affinity with an organic substance having no fluorine atom, and functions as an organic layer composed of an organic compound having a fluorine atom constituting an organic thin film transistor, or has a fluorine The interface of the organic layer composed of the organic compound of the atom has no adverse effect.

The fluorine-containing solvent is preferably composed of carbon, hydrogen, and fluorine, and does not contain atoms other than these. This is because the organic compound having such a fluorine atom is particularly lacking in affinity with an organic substance having no fluorine atom.

As the organic compound having a fluorine atom, an aromatic compound having a fluorine atom is suitably used. This is because the aromatic compound having a fluorine atom dissolves the compound (A) and is excellent in properties.

Among them, a preferred fluorine-containing solvent is an aromatic fluorine compound having 6 to 20 carbon atoms. Examples of the aromatic fluorine compound having 6 to 20 carbon atoms include hexafluorobenzene, pentafluorotoluene, octafluorotoluene, and tetrafluoroanisole. As the fluorine-containing solvent (B), a solvent such as a levelling agent or a surfactant may be added as needed.

In the composition for an organic thin film transistor insulating layer of the present invention, the content of the fluorine-containing solvent (B) is 10 to 3000 parts by weight based on 100 parts by weight of the compound (A) containing a group having a cyclic ether structure. It is preferably 15 to 2000 parts by weight. However, the content of the fluorine-containing solvent (B) may be appropriately determined in consideration of the thickness of the formed organic thin film transistor insulating layer and the type and amount of the resin used in combination with the organic thin film transistor insulating layer composition. Ground adjustment.

<fluororesin (C)>

The composition for an organic thin film transistor insulating layer of the present invention may further contain a fluororesin (C). The fluororesin refers to an organic polymer having a structural unit of a fluorine atom (for example, a repeating unit of a fluorine atom).

The organic thin film transistor insulating layer material is made to contain a fluorine atom-containing organic compound to lower the polarity of the formed insulating layer and to enhance hydrophobicity.

The fluororesin (C) is preferably a functional group having an atom capable of bonding to a surface having a high polarity such as a glass surface or a metal surface. Thereby, the adhesion of the insulating layer containing the fluororesin (C) to glass, metal, or the like is improved.

<Fluororesin (C-1)>

An example of a preferred fluororesin (C) is a fluororesin (C-1) containing a hydroxyl group, for example, a repeating unit represented by the formula (3) and a repeating unit represented by the formula (4).

In the formula (3) showing the structure of the repeating unit contained in the fluororesin (C-1), X represents a monovalent organic group having a fluorine atom of 1 to 20, a fluorine atom or a chlorine atom.

The monovalent organic group having 1 to 20 carbon atoms having a fluorine atom may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a fluorophenyl group or a pentafluorophenyl group.

In one aspect of the repeating unit represented by the formula (3), X is a chlorine atom.

Further, in the formula (4) showing the structure of the repeating unit contained in the fluororesin (C-1), R ₉ represents an alkylene group. The hydrogen atom in the alkylene group may be substituted by a fluorine atom. The alkylene group may, for example, be a methylene group, an ethylene group, a propyl group, a butyl group, a hexyl group or a octyl group.

In one aspect of the repeating unit represented by the formula (4), R ₉ is a butyl group.

The fluororesin (C-1) which can be used in the present invention can be produced, for example, by the following method: a polymerizable monomer which is a raw material of a repeating unit represented by the formula (3), and a formula (4) The polymerizable monomer of the raw material of the repeating unit is subjected to copolymerization using a photopolymerization initiator or a thermal polymerization initiator.

The polymerizable monomer which is a raw material of the repeating unit represented by the formula (3) may, for example, be trifluoroethylene, 1,1,2-trifluoropropene or chlorotrifluoroethylene.

The polymerizable monomer which is a raw material of the repeating unit represented by the formula (4) may, for example, be 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether.

The photopolymerization initiator may, for example, be acetophenone, 2,2-dimethoxy-2-phenylethylbenzene, 2,2-diethoxyethylbenzene, 4-isopropyl 2-hydroxy-2-methylpropenylbenzene, 2-hydroxy-2-methylpropenzene, 4,4'-bis(diethylamino)diphenyl ketone, benzophenone , (o-benzylidene) benzoic acid methyl ester, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, 1-phenyl-1,2-propane Diketo-2-(o-benzylidene) hydrazine, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, diphenyl a carbonyl compound such as benzil, benzil dimethyl ketal, benzil diethyl ketal or diacetyl; an anthracene derivative such as methyl hydrazine or chlorohydrazine; Thioxanthone derivatives such as chlorothioxanthone, 2-methylthiaxanthone, 2-isopropylthioxanthone; diphenyl disulfide, dithiamine A sulfur compound such as dithiocarbamate.

The thermal polymerization initiator may be any initiator which can be a radical polymerization, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobisisoamyl. Nitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane) (1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropane), 2,2'-azobis(2-methylpropionamidine) (2, An azo compound such as 2'-azobis(2-methylpropionamidine) dihydrochloride; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetoxyacetone peroxide, etc. Peroxy ketones; isobutyl peroxide, benzammonium peroxide, 2,4-dichlorobenzhydryl peroxide, o-methylbenzhydryl peroxide, lauryl peroxide, peroxidation Dimethyl fluorenyl peroxides such as chlorobenzhydryl; 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide Hydroperoxides such as peroxylated butyl peroxide; dicumyl peroxide, tributyl cumene peroxide, and third oxidized peroxide Dialkyl peroxide-based and the like; tri (tertiary butyl peroxy) tris Peroxidation of trialkyls such as tris(tert-butylperoxy)triazine; peroxidation of 1,1-di-t-butylcyclohexane, (2,2-di-t-butylperoxide) butane Ketals; tert-butyl peroxypivalate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxyisobutyrate, hexahydrophthalic acid Di-tert-butyl ester, di-tert-butyl peroxydibacate, tert-butyl peroxy 3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate Ester, alkyl perester, such as dibutyl succinate; alkyl perester; diisopropyl peroxydicarbonate, dibutyl phthalate, isopropyl peroxycarbonate A peroxycarbonate such as a third butyl ester.

The fluororesin (C-1) which can be used in the present invention may be a polymerizable monomer which is a raw material of a repeating unit represented by the formula (3) at the time of polymerization, and a repeating unit represented by the formula (4). It is produced from a polymerizable monomer other than the polymerizable monomer of the raw material.

The other polymerizable monomer may, for example, be an unsaturated hydrocarbon and a derivative thereof, a vinyl ether derivative or the like.

The kind of the other polymerizable monomer is appropriately selected depending on the characteristics required for the insulating layer such as the protective insulating layer. One of the preferred aspects of the other polymerizable monomer is a monomer having no active hydrogen, such as a monomer having an alkyl group or the like.

Examples of the unsaturated hydrocarbon and its derivative include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, ethylene chloride, allyl alcohol and the like.

The vinyl ether derivative may, for example, be methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether or phenyl vinyl ether.

Among these, butyl vinyl ether and cyclohexyl vinyl ether are preferable.

The amount of the polymerizable monomer used as the raw material of the repeating unit represented by the formula (3) is adjusted so that the amount of fluorine introduced into the fluororesin (C-1) is an appropriate amount.

The fluororesin (C-1) which can be used in the invention may, for example, be poly(trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-ethyl vinyl ether) or poly(trifluoroethylene-co-) 4-hydroxybutyl vinyl ether-co-butyl vinyl ether), poly(trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-3-chloromethylphenyl vinyl ether), poly (Trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-cinnamic acid vinyl ester) and the like.

<Fluororesin (C-2)>

Other examples of the preferred fluororesin (C) include those having a functional group reactive with active hydrogen, such as a fluororesin (C-2), which contains a repeating unit represented by the formula (5) and contains two or more first members. A functional group which is a functional group which generates a second functional group which reacts with active hydrogen by the action of electromagnetic waves or heat.

In the formula (5) showing the structure of the repeating unit contained in the fluororesin (C-2), R ₁₀ to R ₁₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 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. Raa represents a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group may be substituted by a fluorine atom. a represents an integer of 0 to 20, and m represents an integer of 1 to 5. When Raa is plural, the same may be the same or different. When R is plural, the numbers may be the same or may be different. When Rf is plural, the numbers may be the same or may be different.

The divalent organic group having 1 to 20 carbon atoms may be any of a straight chain, a branched group, and a cyclic group, and may be an aliphatic hydrocarbon or an aromatic hydrocarbon, and may also contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. . 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, a divalent cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and an alkyl group may be mentioned. A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -O-CO-, -O-, -CO-NH-, -NH-CO-NH-, or -NH-CO-O-. These groups may also have a substituent. 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 aliphatic hydrocarbon group having 3 to 6 carbon atoms are preferable. a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms substituted by an alkyl group or the like, -O-CO-.

The divalent linear aliphatic hydrocarbon group, the divalent branched aliphatic hydrocarbon group, and the divalent cyclic aliphatic hydrocarbon group may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. , isopropyl, isobutyl, dimethyl propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and examples thereof include a phenyl group, a naphthyl group, a decyl group, a dimethylphenyl group, a trimethylphenyl group, and an ethyl benzene group. Base, diethyl phenyl, triethyl phenyl, propyl phenyl, butyl phenyl, methyl anthranyl, dimethylnaphthyl, trimethyl stilbene, vinyl Vinnaphthylene, ethenylnaphthylene, methyl thiol, ethyl thiol and the like.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁₀ to R ₁₂ include the same groups as those of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁ . An example of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by Rf is, for example, the same group as the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by X.

The monovalent organic group having 1 to 20 carbon atoms represented by R may, for example, be a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a ring having 3 to 20 carbon atoms. The aliphatic hydrocarbon group and the aromatic hydrocarbon group having 6 to 20 carbon atoms are preferably a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a ring having 3 to 6 carbon atoms. An aliphatic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

A monovalent organic group having 1 to 20 carbon atoms which may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and a ring. Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, phenyl, naphthyl, anthracenyl, tolyl, xylyl, dimethylphenyl, trimethylbenzene Base, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butylphenyl, methylnaphthyl, dimethylnaphthyl, trimethylnaphthyl, vinylnaphthyl , methyl fluorenyl, ethyl fluorenyl, chlorophenyl, bromophenyl and the like.

In one aspect of the repeating unit represented by the formula (5), R ₁₀ to R ₁₂ are a hydrogen atom, Rf is a fluorine atom, a is 0, and m is 5.

The fluororesin (C-2) which can also be used in the present invention contains a repeating unit represented by the formula (5) and contains two or more first functional groups containing irradiation or heat by electromagnetic waves. Acting to form a functional group of a second functional group that reacts with active hydrogen.

The active hydrogen means a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

The second functional group that reacts with the active hydrogen is preferably protected (closed) before being heated in the step of forming the gate insulating layer. That is, the first functional group is preferably deprotected by heat to form a second functional group that reacts with active hydrogen. This is because the storage stability of the composition can be improved.

The first functional group may, for example, be an isocyanato group blocked with a blocking agent or an isothiocyanate group blocked by a blocking agent.

The above-mentioned isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent can have an activity of reacting only with one isocyanate group or isothiocyanate group in the molecule of the blocking agent 1 A hydrogen blocking agent is produced by reacting with an isocyanato group or an isothiocyanate group.

The above blocking agent preferably dissociates at a temperature of 170 ° C or lower even after reacting with an isocyanate group or an isothiocyanate group. Examples of the blocking agent include an alcohol compound, a phenol compound, an active methylene compound, a thiol compound, a guanamine compound, a quinone compound, an imidazole compound, a urea compound, and an oxime compound. An amine compound, an imine compound, a bisulfite salt, a pyridine compound, or a pyrazole compound. These blocking agents may be used singly or in combination of two or more. Preferred examples of the blocking agent include a quinone compound and a pyrazole compound.

Hereinafter, a specific blocking agent will be exemplified. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cyanisol, methyl carbitol, and benzene. Methanol, cyclohexanol, etc. Examples of the phenolic compound include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoate. Examples of the active methylene group compound include dimethyl malonate, diethyl malonate, methyl acetonitrile acetate, ethyl acetate ethyl acetate, and acetylacetone. Examples of the thiol compound include butyl mercaptan and dodecyl mercaptan. Examples of the guanamine-based compound include acetanilide, acetamide, ε-caprolactam, δ-valeroinamide, γ-butylidene, and the like, and the quinone imine compound may, for example, be butyl. Diimine, maleimide, and the like. Examples of the imidazole-based compound include imidazole and 2-methylimidazole. Examples of the urea-based compound include urea, thiourea, and ethylene urea. Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketone oxime, cyclohexanone oxime, and the like. The amine compound may, for example, be diphenylamine, aniline or carbazole. The imine compound may, for example, be an ethyleneimine or a polyethylenimine. The bisulfite salt may, for example, be sodium bisulfite. Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline. The pyrazole-based compound may, for example, be 3,5-dimethylpyrazole or 3,5-diethylpyrazole.

The isocyanate group blocked by a blocking agent which can be used in the present invention is preferably a group represented by the formula (6), and Xa is a group of an oxygen atom, a group represented by the formula (7), and Xb is a group of an oxygen atom. The isothiocyanate group blocked by a blocking agent which is preferably used in the present invention, preferably a group represented by the formula (6), and a group in which Xa is a sulfur atom, a group represented by the formula (7), and a group in which Xb is a sulfur atom .

In the formula (6), Xa represents an oxygen atom or a sulfur atom, and R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁₃ and R ₁₄ include the same groups as the examples of the monovalent organic group represented by R ₁₀ to R ₁₂ .

In one aspect of the repeating unit represented by the formula (6), Xa is an oxygen atom, R ₁₃ is a methyl group, and R ₁₄ is an ethyl group.

In the formula (7), Xb represents an oxygen atom or a sulfur atom, and R ₁₅ , R ₁₆ and R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁₅ , R ₁₆ and R ₁₇ include the same groups as those of the monovalent organic group represented by R ₁₀ to R ₁₂ .

In one aspect of the repeating unit represented by the formula (7), Xb is an oxygen atom, and R ₁₅ to R ₁₇ are a hydrogen atom.

The isocyanato group blocked by the blocking agent may, for example, be an O-(methylidyneamino)carboxyamino group, an O-(1-ethylideneamino)carboxyamino group, or O. -(1-methylethylideneamino)carboxyamino, O-[1-methylpropyleneamino]carboxyamino, (N-3,5-dimethylpyrazolylcarbonyl)amine (N-3-ethyl-5-methylpyrazolylcarbonyl)amino, (N-3,5-diethylpyrazolylcarbonyl)amine, (N-3-propyl-5-A (pyridazolylcarbonyl)amino, (N-3-ethyl-5-propylpyrazolylcarbonyl)amino.

The isothiocyanate group blocked by the blocking agent may, for example, be O-(methyleneamino)thiocarboxyamino group, O-(1-ethylideneamino)thiocarboxyamino group, O-(1-A Isoethylamino)thiocarboxyamino, O-[1-methylpropyleneamino]thiocarboxyamino, (N-3,5-dimethylpyrazolylthiocarbonyl)amine, N-3-ethyl-5-methylpyrazolylthiocarbonyl)amine, (N-3,5-diethylpyrazolylthiocarbonyl)amine, (N-3-propyl-5-A (pyridazolylthiocarbonyl)amino group, (N-3-ethyl-5-propylpyrazolylthiocarbonyl)amino group.

The first functional group used in the present invention is preferably an isocyanate group blocked by a blocking agent.

Next, a method for producing the fluororesin (C-2) used in the present invention will be described. The fluororesin (C-2) can be produced, for example, by using a polymerizable monomer which is a raw material of a repeating unit represented by the formula (5) and a polymerizable monomer containing a first functional group, and uses light. A method of copolymerizing a polymerization initiator or a thermal polymerization initiator.

The photopolymerization initiator and the thermal polymerization initiator may, for example, be the same photopolymerization initiator and thermal polymerization initiator which can be used in the production of the fluororesin (C-1).

The polymerizable monomer which is a raw material of the repeating unit represented by the formula (5) may, for example, be 2-trifluoromethylstyrene, 3-trifluoromethylstyrene or 4-trifluoromethylstyrene; 3,4,5,6-pentafluorostyrene, 4-fluoromethylstyrene, and the like.

The polymerizable monomer containing a first functional group may, for example, be an isocyanato group blocked with a blocking agent or an isothiocyanate group blocked by a blocking agent and a monomer having an unsaturated bond. The isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturatedly bonded monomer can have an isocyanato group or an isothiocyanate group and an unsaturated bond. The compound is produced by reacting with a blocking agent. The unsaturated bond is preferably an unsaturated double bond.

The compound having an unsaturated double bond and an isocyanate group may, for example, be 2-propenyloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate or 2-(2'-methacryloxyloxy group. Ethyl) oxyethyl isocyanate or the like. The compound having an unsaturated double bond and an isothiocyanate group may, for example, be 2-propenyloxyethyl isothiocyanate, 2-methylpropenyloxyethyl isothiocyanate or 2-( 2'-Methyl propylene methoxyethyl) oxyethyl isothiocyanate.

The blocking agent can be suitably used as the aforementioned blocking agent. When a monomer having an isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturated bond is produced, an organic solvent, a catalyst, or the like may be added as needed.

The monomer having an unsaturated double bond and an isocyanate group blocked by a blocking agent may, for example, be 2-[O-[1'-methylpropyleneamino]carboxyamino]ethyl methacrylate. 2-[N-[1',3'-dimethylpyrazolyl]carboxyamino]ethyl methacrylate, 2-[O-[1'-methylpropyleneamino] methacrylate Carboxyamino]ethyl ester, 2-[N-[1',3'-dimethylpyrazolyl]thiocarboxyamino]ethyl methacrylate, and the like.

The fluororesin (C-2) which can be used in the present invention may be a polymerizable monomer which is a raw material of a repeating unit represented by the formula (5) and a polymerizable monomer other than the first functional group. Other polymerizable monomers are manufactured.

Examples of the other polymerizable monomer include acrylates and derivatives thereof, methacrylates and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, Acrylonitrile and its derivatives, vinyl esters and derivatives of organic carboxylic acids, allyl esters of organic carboxylic acids and their derivatives, dialkyl esters of fumaric acid and their derivatives, cis-butane a dialkyl ester of a maleic acid and a derivative thereof, a dialkyl ester of a methylene succinic acid and a derivative thereof, an N-vinylamine derivative of an organic carboxylic acid, a maleene Diterpene imine and its derivatives, terminally unsaturated hydrocarbons and derivatives thereof, and organic sulfonium compounds containing unsaturated bonds.

The kind of the other polymerizable monomer is appropriately selected depending on the characteristics required for the insulating layer. From the viewpoint of excellent durability and a decrease in hysteresis of the organic thin film transistor, a monomer having a high molecular density such as styrene or a styrene derivative and forming a hard film is selected.

Further, from the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode and the surface of the substrate, a single sheet such as methacrylate or a derivative thereof, an acrylate or a derivative thereof, and the like is selected for imparting flexibility. body. In a preferred embodiment, a monomer having no active hydrogen-containing group such as an alkyl (meth) acrylate such as a methyl group or an ethyl group is selected.

For example, a polymerizable monomer which is a raw material of the repeating unit represented by the formula (5) and a styrene or styrene derivative which does not have an active hydrogen-containing group are combined and polymerized to obtain a fluororesin, and then the fluorine is obtained. When the resin is used for a composition for an organic thin film transistor insulating layer, a gate insulating layer having high durability and low hysteresis is obtained.

As the acrylate and its derivative, a monofunctional acrylate may be used, and although the amount used may be limited, a polyfunctional acrylate may also be used, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. Propyl ester, n-butyl acrylate, isobutyl acrylate, dibutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, cyclohexyl acrylate, acrylic acid Phenyl ester, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl ethyl acrylate, ethylene glycol diacrylate Ester, propylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate Ester, pentaerythritol pentaacrylate, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N-acryloylmorpholine, acrylic acid 2 , 2,2-trifluoroethyl ester, acrylic acid 2,2,3 ,3,3-pentafluoropropyl ester, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-(perfluorohexyl)ethyl acrylate, acrylic acid 3- Perfluorohexyl-2-hydroxypropyl ester, 2-(perfluorooctyl)ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl acrylate, acrylic acid 2 -(perfluoro-3-methylbutyl)ethyl ester, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, acrylic acid 2-(Perfluoro-3-methylbutyl)-2-hydroxypropyl ester, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro 7-methyloctyl acrylate) Ethyl ester, 3-(perfluoro 7-methyloctyl)-2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, acrylic acid 1H ,1H,7H-dodecafluorobutyl ester, 1H,1H,9H-hexadecafluorodecyl acrylate, 1H-1-(trifluoromethyl)trifluoroethyl acrylate, 1H,1H,3H-hexafluorobutyl acrylate Ester and the like.

A monofunctional methacrylate can be used for the methacrylate and its derivative, and a polyfunctional methacrylate can also be used although the amount used is limited, and for example, methyl methacrylate or methacrylic acid B can be used. Ester, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate Ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, ethylene glycol dimethacrylate, propylene glycol Dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, Trimethylolpropane trimethacrylate, pentaerythritol Methacrylate, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N-methylpropenylmorpholine, methacrylic acid 2,2,2- Trifluoroethyl ester, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2-hydroxy methacrylate Propyl ester, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-methacrylic acid Perfluorooctyl-2-hydroxypropyl ester, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 3-(meth) Fluorinated 3-methylbutyl)-2-hydroxypropyl ester, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)-2-methacrylate Hydroxypropyl ester, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro 7-methyloctyl)ethyl methacrylate, 3-(meth) Fluorine 7-methyloctyl)-2-hydroxypropyl ester, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H methacrylate 7H-dodecyl butyl acrylate, methacryl 1H, 1H, 9H- hexadecafluoro-nonyl methacrylate, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H- hexafluoro-butyl.

Examples of styrene and its derivatives include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, and 2,5-dimethyl styrene. , 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-three Methylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, Bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinyl linkage Benzene, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinyl anthracene, α-methylbenzene Ethylene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-Dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethyl Styrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4-aminostyrene, and the like.

Examples of the acrylonitrile and derivatives thereof include acrylonitrile and the like. The methacrylonitrile and its derivative may, for example, be methacrylonitrile or the like.

The vinyl ester of an organic carboxylic acid and its derivative may, for example, be vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate or divinyl adipate.

The allyl ester of an organic carboxylic acid and a derivative thereof may, for example, be allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate or diallyl isophthalate. Ester, diallyl phthalate, and the like.

The dialkyl ester of fumaric acid and derivatives thereof may, for example, be dimethyl fumarate, diethyl fumarate, diisopropyl fumarate or fumaric acid. 2. Second butyl ester, diisobutyl methacrylate, di-n-butyl fumarate, di 2-ethylhexyl fumarate, diphenyl methyl fumarate, and the like.

The dialkyl ester of maleic acid and derivatives thereof may, for example, be dimethyl maleate, diethyl maleate, diisopropyl maleate or maleic acid. Dibutyl acrylate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, diphenylmethyl maleate, and the like.

Examples of the dialkyl ester of methylene succinic acid and derivatives thereof include dimethyl methylene succinate, diethyl methylene succinate, diisopropyl methylene succinate, and sub Dibutyl succinate, diisobutyl methylene succinate, di-n-butyl methylene succinate, di-ethylhexyl methylene succinate, methylene Diphenyl succinate and the like.

The N-vinylamine derivative of the organic carboxylic acid may, for example, be N-methyl-N-vinylacetamide or the like.

The maleimide and its derivative may, for example, be N-phenyl maleimide or N-cyclohexylmethyleneimine.

The terminally unsaturated hydrocarbon and its derivative may, for example, be 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, ethylene chloride or allyl alcohol.

The organic ruthenium compound containing an unsaturated bond may, for example, be allyltrimethylsulfonium, allyltriethylsulfonium, allyltributylphosphonium, trimethylvinylsulfonium, triethylvinylfluorene. Wait.

Among these, an alkyl acrylate, an alkyl methacrylate, styrene, acrylonitrile, methacrylonitrile, allyl trimethyl hydrazine is preferable.

The amount of fluorine introduced into the fluororesin (C) is preferably from 1 to 60% by mass, more preferably from 5 to 50% by mass, even more preferably from 5 to 40% by mass, based on the mass of the polymer compound. When the amount of fluorine is less than 1% by mass or more than 60% by mass, the compatibility with the fluorine-containing solvent (B) is deteriorated, and the preparation of the composition becomes difficult.

The fluororesin (C) is preferably a polymer compound having a weight average molecular weight of 3,000 to 1,000,000, more preferably a polymer compound having a weight average molecular weight of 5,000 to 500,000. The fluororesin (C) may be any of a linear chain, a branched chain, and a cyclic chain.

<Cationic polymerization initiator>

In the composition for an organic thin film transistor insulating layer of the present invention, it is preferred to further add a photocationic polymerization initiator or a thermal cationic polymerization initiator. This is because the ring-opening addition reaction of the cyclic ether structure contained in the compound (A) is more easily carried out.

The photocationic polymerization initiator and the thermal cationic polymerization initiator may, for example, be a phosphonium salt or a phosphonium salt.

The onium salt may, for example, be diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate or tolylphenylpyridinium tetrakis(pentafluorophenyl)borate.

The phosphonium salt may, for example, be triphenylphosphonium phosphate, (phenylthio)phenyldiphenylphosphonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate or (phenylthio)phenyldiphenyl hexafluoroantimonate. Base, bis(hexafluoroantimonate) 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]phenyl sulfide, 4-[4-(4-t-butylbenzene) hexafluorophosphate Mercapto)phenylthio]phenylbis(4-methylphenyl)anthracene.

Specifically, the photocationic polymerization initiator is, for example, a trade name of Rhodorsil 2074 (manufactured by Rhodia Japan Co., Ltd.), a product name of ADEKA OPTOMER-SP-150 (manufactured by Adeka Co., Ltd.), and a trade name of ADEKA OPTOMER. - SP-152 (made by ADEKA CORPORATION), trade name ADEKA OPTOMER-SP-170 (made by Adeka Co., Ltd.), brand name ADEKA OPTOMER-SP-172 (made by Adeka Co., Ltd.), etc. Further, an onium salt compound described in JP-A-9-118663 can also be used.

Specifically, the thermal cationic polymerization initiator may, for example, be a product name ADEKA OPTON-CP series (made by ADEKA CORPORATION).

The ratio of the photocationic polymerization initiator or the thermal cationic polymerization initiator in the composition for an organic thin film transistor insulating layer of the present invention is 100 weights based on the compound (A) having a group having a cyclic ether structure. The portion is preferably in the range of 0.0001 to 30 parts by weight, more preferably in the range of 0.001 to 10 parts by weight. Further, two or more kinds of the photocationic polymerization initiator or the thermal cationic polymerization initiator may be used.

The organic thin film of the present invention is obtained by mixing a compound (A) having a group having a cyclic ether structure, a fluorine-containing solvent (B), and optionally a fluororesin (C) with a cationic polymerization initiator or the like. A composition for a transistor insulating layer.

When the fluororesin (C) is contained in the composition for an organic thin film transistor insulating layer of the present invention, the content thereof is 600 parts by weight or less, preferably 100 to 500 parts by weight based on 100 parts by weight of the compound (A). Share.

When the content of the fluororesin (C) in the composition for an organic thin film transistor insulating layer exceeds 600 parts by weight based on 100 parts by weight of the compound (A), the solvent resistance of the organic thin film transistor insulating layer is lowered.

When the fluororesin (C-1) having a hydroxyl group is used as the fluororesin (C), the content of the fluororesin (C-1) in the composition for an organic thin film transistor insulating layer of the present invention is relative to the compound (A). It is 50 to 600 parts by weight, preferably 100 to 500 parts by weight, more preferably 200 to 400 parts by weight, per 100 parts by weight.

When the content of the fluororesin (C-1) in the composition for an organic thin film transistor insulating layer is less than 50 parts by weight based on 100 parts by weight of the compound (A), aggregation of the coating film may occur during drying. When it exceeds 600 parts by weight, the solvent resistance of the organic thin film transistor insulating layer is lowered.

In addition, the content of the fluorine-containing solvent (B) in the composition for an organic thin film transistor insulating layer is 100 to 3000 parts by weight, preferably 500 to 2,000 parts by weight based on 100 parts by weight of the compound (A). The parts by weight are more preferably from 800 to 1,500 parts by weight.

When the content of the fluorine-containing solvent (B) in the composition for an organic thin film transistor insulating layer is less than 100 parts by weight based on 100 parts by weight of the compound (A), the flatness of the coating film is lowered to more than 3,000 by weight. At the time of the application, the organic thin film transistor insulating layer may generate a pin hole.

The fluororesin (C) can also be used by mixing a fluororesin (C-1) having a hydroxyl group and a fluororesin (C-2) containing a functional group reactive with active hydrogen. Since the functional groups contained in the fluororesin (C-1) and the fluororesin (C-2) react with each other to form a crosslinked structure in the interior of the organic thin film transistor insulating layer, polarization of the insulating layer is suppressed, and solvent resistance is obtained. Sex becomes higher.

The composition for an organic thin film transistor insulating layer of the present invention is a composition used in forming an insulating layer included in an organic thin film transistor. The composition for an organic thin film transistor insulating layer is, for example, a composition for an organic thin film transistor protective layer used for forming a protective layer, or a composition for an organic thin film transistor gate insulating layer used for forming a gate insulating layer. . The composition for the organic thin film transistor insulating layer is preferably a protective layer for forming an organic thin film transistor.

The protective layer formed using the composition for an organic thin film transistor insulating layer of the present invention is excellent in insulation and airtightness. Therefore, the organic thin film transistor having the protective layer is stably driven even in the atmosphere by effectively isolating the organic semiconductor compound contained in the transistor from the surrounding environment.

(Organic thin film transistor)

Fig. 1 is a schematic cross-sectional view showing the structure of a bottom gate top contact type 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, and an organic semiconductor layer 4 formed on the gate insulating layer 3. The source electrode 5 and the drain electrode 6 of the channel portion are sandwiched on the organic semiconductor layer 4, and the insulating layer 7 is covered by the entire covering member.

The bottom gate top contact type organic thin film transistor can be manufactured, for example, by forming a gate electrode on the substrate, forming a gate insulating layer on the gate electrode, and forming an organic semiconductor layer on the gate insulating layer. After forming a source electrode and a drain electrode on the organic semiconductor layer, a protective insulating layer is formed and manufactured.

Fig. 2 is a schematic cross-sectional view showing the structure of a bottom gate bottom contact type 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, and a source formed on the gate insulating layer 3 and blocking the channel portion. The electrode electrode 5 and the drain electrode 6, the organic semiconductor layer 4 formed on the source electrode 5 and the drain electrode 6, and the protective insulating layer 7 covering the entire element.

The bottom gate bottom contact type organic thin film transistor can be manufactured, for example, by forming a gate electrode on the substrate, forming a gate insulating layer on the gate electrode, and forming a source electrode on the gate insulating layer. And a drain electrode is formed by forming an organic semiconductor layer on the source electrode and the drain electrode to form a protective insulating layer.

The formation of the protective insulating layer is carried out by applying the composition for a protective insulating layer of the present invention to the organic semiconductor layer, and drying and hardening.

The composition for a protective insulating layer can be applied onto an organic semiconductor layer by a conventional spin coating method, die coating method, screen printing method, inkjet printing method, or the like.

The substrate 1, the gate electrode 2, the source electrode 5, the drain electrode 6, and the organic semiconductor layer 4 constituting the organic thin film transistor can be formed by a commonly used material and method. For example, the material of the substrate is a resin, a plastic plate, a film, a glass plate, a slab, or the like. The material of the electrode is formed by a conventional method such as a vapor deposition method, a sputtering method, a printing method, or an inkjet printing method using chromium, gold, silver, aluminum or the like.

As the organic semiconductor compound, a π-conjugated polymer is widely used, and for example, polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles can be used. ), poly(p-phenylenevinylene) (poly(p-phenylenevinylene)).

Further, examples of the low molecular substance having solubility in an organic solvent include polycyclic aromatic derivatives such as pentacene, phthalocyanine derivatives, perylene derivatives, and tetrathiavir. A tetrathiafulvalene derivative, a tetracyanoquinodimethane derivative, a fullerene, or a carbon nanotube. Specifically, for example, a condensate of 9,9-di-n-octylindole-2,7-di(ethyl borate) and 5,5'-dibromo-2,2'-bithiophene can be mentioned.

The formation of the organic semiconductor layer can be carried out, for example, by adding a solvent or the like to the organic semiconductor compound, preparing an organic semiconductor coating liquid, applying it to the gate insulating layer, and drying it.

The solvent to be used is not particularly limited as long as it dissolves or disperses the organic semiconductor compound, and is preferably a solvent having a boiling point of from 50 ° C to 200 ° C at normal pressure. The solvent may, for example, be chloroform, toluene, anisole, 2-heptanone or propylene glycol monomethyl ether acetate. The organic semiconductor coating liquid can be applied to the gate insulating layer by a conventional spin coating method, die coating method, screen printing method, inkjet printing method, or the like, similarly to the above-described insulating layer coating liquid. on.

With the organic thin film transistor of the present invention, a member for a display having an organic thin film transistor can be suitably produced. A display member having a display member can be suitably used by using the member for a display having an organic thin film transistor.

[Examples]

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

Synthesis Example 1 (Synthesis of Polymer Compound 1)

Mix 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (2,7-bis (1,3, in an inert atmosphere) 2-dioxaborolan-2-yl)-9,9-dioctylfluorene) 5.20 g, bis(4-bromophenyl)-(4-t-butylphenyl)amine 4.50 g, palladium acetate 2.2 mg, tris(2- 15.1 mg of methylphenylphosphine oxide, 0.91 g of methyltrioctyl ammonium chloride (manufactured by Aldrich, trade name "Aliquat 336" (registered trademark)), and 70 ml of toluene were heated to 105 °C. To the reaction solution, 19 ml of a 2 mol/kg sodium carbonate aqueous solution was added dropwise, and the mixture was refluxed for 4 hours. Then, 121 mg of phenylboric acid was added, followed by reflux for 3 hours. Then, an aqueous solution of sodium diethyldithiocarbamate was added, and the mixture was stirred at 80 ° C for 4 hours. After cooling, it was washed three times with water (60 ml), washed three times with 3% by weight aqueous acetic acid solution (60 ml), and washed three times with water (60 ml) by passing through an alumina column and a rubber tube. Refined by column. The obtained toluene solution was added dropwise to methanol (3 liters), and after stirring for 3 hours, the obtained solid was filtered and dried. The yield of the obtained polymer compound 1 represented by the following formula was 5.25 g. Here, n in the following formula represents the degree of polymerization.

Polymer compound 1

The weight average molecular weight of the polymer compound 1 obtained from the standard polystyrene was 2.6 × 10 ⁵ . The measurement conditions of the weight average molecular weight were as follows: GPC manufactured by Shimadzu Corporation, one column of "Tskgel super HM-H" + one "Tskgel super H2000", and a mobile phase: THF.

Synthesis Example 2 (Synthesis of Polymer Compound 2)

2,3,4,5,6-pentafluorostyrene (made by Aldrich) 2.00 g, 2,2'-azobis(2-methylpropionitrile) 0.01 g, 2,3,4,5,6 - 3.50 g of pentafluorotoluene (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 50 ml pressure-resistant container (manufactured by ACE), bubbled with argon, sealed tightly, and polymerized in an oil bath at 60 ° C for 24 hours to obtain the following formula. The polymer compound 2 is a 2,3,4,5,6-pentafluorotoluene solution. Here, n in the following formula represents the degree of polymerization.

Polymer compound 2

The weight average molecular weight of the obtained polymer compound 2 obtained from standard polystyrene was 88,000. The measurement conditions of the weight average molecular weight are the same as those described in Synthesis Example 1.

Example 1 (Preparation of Composition 1 for Organic Thin Film Oxide Insulation Layer)

2,3,4,5,6-pentafluorotoluene solution 2.00 g containing 40% by weight of "Lumiflon (registered trademark) LF200F" (manufactured by Asahi Glass Co., Ltd., OH price: 45 mgKOH/g) was placed in a 20 ml sample vial. "ARONE OXETANE (registered trademark) OXT-221" (manufactured by Toagosei Co., Ltd.) 0.27g, "Rhodorsil (registered trademark) 2074" (manufactured by Rhodia Japan Co., Ltd.) 0.00054g, 2,3,4,5,6-pentafluorotoluene 2.00 g of a solution (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and prepared to prepare a solution. The obtained solution was filtered through a membrane filter having a pore size of 0.45 μm to prepare a composition 1 for an organic thin film transistor insulating layer.

"ARONE OXETANE (registered trademark) OXT-221" is a compound having a structure shown by the following formula.

"Lumiflon (registered trademark) LF200F" is a polymer compound having a repeating unit represented by the formula (2-a) and a repeating unit represented by the formula (3-a). In the formula (2-a), X represents a fluorine atom, a chlorine atom or a trifluoromethyl group. In the formula (3-a), R ₄ represents an alkylene group.

(Production of field effect type organic thin film transistor)

The polymer compound 1 was dissolved in xylene to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and the solution was filtered through a membrane filter having a pore size of 0.45 μm to prepare a coating liquid.

The obtained coating liquid containing the polymer compound 1 was applied onto a bottom gate contact element (manufactured by Co., Ltd.) by a spin coating method, and dried at 200 ° C for 10 minutes in nitrogen to form a thickness of about 60 nm. Active layer.

Then, on the obtained active layer, the composition 1 for an organic thin film transistor insulating layer was applied by a spin coating method. Then, it was dried at 50 ° C for 5 minutes, and irradiated with ultraviolet rays (254 nm) for 1 minute in a argon atmosphere using a UV/ozone purifier (Model UV-1, manufactured by SAMCO). Then, it was calcined at 100 ° C for 30 minutes to form a protective insulating layer having a thickness of about 4 μm to prepare a field effect type organic thin film transistor 1.

<Chip Characteristics>

For the field effect type organic thin film transistor 1 produced, the transistor characteristics were measured in the atmosphere. Vacuum probe (BCT22MDC-5-HT-SCU; Changyi Electronic Instrument Service) is used to make the gate voltage Vg in the range of 20 to -40 V and the source ‧ 汲 voltage Vsd vary from 0 to -40 V The company's system) measures its crystal characteristics in the atmosphere. The measured threshold voltage (Vth) is shown in Table 1.

Comparative Example 1 (Production of Field Effect Organic Thin Film Transistor)

Add 1.00 g of 2,3,4,5,6-pentafluorotoluene solution to 1.00 g of 2,3,4,5,6-pentafluorotoluene solution of polymer compound 2 and filter with a membrane having a pore size of 0.45 μm. A field effect type organic thin film transistor was produced in the same manner as in Example 1 except that the composition 1 for the organic thin film transistor insulating layer prepared by the filtration was used instead of the composition 1 for the organic thin film transistor insulating layer, and the transistor was measured in the atmosphere. characteristic. The thickness of the protective insulating layer is about 6 μm. The absolute value of the threshold voltage is 40 V or more, so that the gate voltage Vg is in the range of 20 to -40 V and the source ‧ drain voltage Vsd is changed from 0 to -40 V, and cannot be driven.

1. . . Substrate

2. . . Gate electrode

3. . . Gate insulation

4. . . Organic semiconductor layer

5. . . Source electrode

6. . . Bipolar electrode

7. . . The protective layer

Fig. 1 is a schematic cross-sectional view showing the structure of a bottom gate top contact type organic thin film transistor according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing the structure of a bottom gate bottom contact type organic thin film transistor according to another embodiment of the present invention.

1. . . Substrate

2. . . Gate electrode

3. . . Gate insulation

4. . . Organic semiconductor layer

5. . . Source electrode

6. . . Bipolar electrode

7. . . The protective layer

Claims (10)

A composition for an organic thin film transistor insulating layer, comprising: a compound (A) having a group having a cyclic ether structure; and a fluorine-containing solvent (B), wherein the group having a cyclic ether structure is selected from the group consisting of 1) at least one of the group shown and the group represented by the formula (2); Wherein R ₁ to R ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; the hydrogen atom in the organic group may be substituted by a fluorine atom; In the formula, R ₄ to R ₈ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; the hydrogen atom in the organic group may be substituted by a fluorine atom; the fluorine-containing solvent is a carbon having a carbon number of 6 to 20 Fluorine compounds. The composition for an organic thin film transistor insulating layer according to claim 1, further comprising a fluororesin (C). The composition for an organic thin film transistor insulating layer according to the second aspect of the invention, wherein the fluororesin (C) is a fluororesin (C-1) selected from the following and a fluororesin (C) as defined below. -2) at least one fluororesin in the group; fluororesin (C-1): a fluororesin containing a repeating unit represented by the formula (3) and a repeating unit represented by the formula (4); In the formula, X represents a monovalent organic group having a fluorine atom of 1 to 20, a fluorine atom or a chlorine atom; Wherein R ₉ represents an alkylene group selected from the group consisting of a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group; a hydrogen atom in the alkyl group; a fluororesin (C-2): a fluororesin containing a repeating unit represented by the formula (5) and containing two or more first functional groups, wherein the first functional group is caused by electromagnetic waves Or a functional group that generates a second functional group that reacts with active hydrogen; Wherein R ₁₀ to R ₁₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; a hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted by a fluorine atom; and 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; and Raa represents a divalent organic group having 1 to 20 carbon atoms; The hydrogen atom may be substituted by a fluorine atom; a represents an integer of 0 to 20, m represents an integer of 1 to 5; when Raa is plural, the same may be the same or different; when R is plural, The same may be the same or different; when Rf is plural, the same may be the same or different. The composition for an organic thin film transistor insulating layer according to claim 3, wherein the first functional group is selected from an isocyanato group blocked by a blocking agent and blocked by a blocking agent. At least one group in the group of isothiocyanato. The composition for an organic thin film transistor insulating layer according to claim 3, wherein the first functional group is a group represented by the formula (6); In the formula, Xa represents an oxygen atom or a sulfur atom; and R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The composition for an organic thin film transistor insulating layer according to claim 3, wherein the first functional group is a group represented by the formula (7); In the formula, Xb represents an oxygen atom or a sulfur atom; and R ₁₅ , R ₁₆ and R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. An organic thin film transistor having: a source electrode; a drain electrode; a gate electrode; an organic semiconductor layer; and an organic thin film transistor insulating layer according to any one of claims 1 to 6. An insulating layer formed of the composition. The organic thin film transistor according to claim 7, wherein the insulating layer is an overcoat insulating layer. A member for a display comprising: the organic thin film transistor according to claim 7 or 8. A display comprising: the member for a display according to claim 9 of the patent application.