TW201219376A - Composition for insulation layer of organic thin film transistor and organic thin film transistor - Google Patents

Abstract

An objective of this invention is to provide a composition for insulation layer of organic thin film transistor capable of manufacturing an organic thin film transistor having a small absolute value of threshold voltage when it is driven in the atmosphere. To attain this objective, this invention provide a composition for insulation layer of organic thin film transistor containing a compound (A) containing a group having a cyclic ether structure in a molecule, and a fluorine-containing solvent (B).

Description

201219376 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for an organic thin film transistor insulating layer suitable for forming an insulating layer provided in an organic thin film transistor, and particularly relates to an overcoat suitable for formation A composition for an organic thin film transistor insulating layer of an insulating layer. [Prior Art] Since an organic thin film transistor can be manufactured at a lower temperature than an inorganic semi-conductor, a plastic substrate or a thin film can be used as a substrate thereof, and by using such a substrate, flexibility and lightness can be obtained. Components that are not easily damaged. Further, by forming a film by a coating or printing method 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. Further, since the types of materials that can be used for review of the crystal are very rich, 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 a 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 crystal characteristics are liable to cause deterioration over time due to humidity, oxygen, and the like. Therefore, in the bottom gate type (bottom 3 323440 201219376 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 external gases. contact. On the other hand, in the top gate type organic field effect transistor device structure, the organic semiconductor compound is protected by the gate insulating layer. Thus, in order to form a protective insulating layer or a gate insulating layer which covers 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 proposed to contain a copolymer of tetrafluoroethylene (Patent Document 1). [PRIOR ART DOCUMENT] [Patent Document] Japanese Patent Application Laid-Open No. 2005-513788. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] 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 charge, and increases the absolute value of the threshold voltage. Therefore, the organic % effect transistor including the insulating layer formed using the above-mentioned organic thin film transistor insulating layer material has a problem that the absolute value of the threshold voltage at the time of driving in the atmosphere A is large. 323440 g 201219376 An object of the present invention is to provide an organic thin film transistor for a composition of an organic thin film transistor insulating layer which can produce an organic film having a small absolute value of a threshold voltage when driven in the atmosphere. [Means for Solving the Problem] The present invention provides a composition for an organic thin film transistor insulating layer, which comprises a compound (A) having a group having a cyclic ether structure and a fluorine-containing solvent (B). In the above 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, 匕 to R3 each independently represent a hydrogen atom or a monovalent organic having a carbon number of i to 2 Å. The hydrogen source of the silk scarf is replaced by (four) sub]

XX X: (2) [In the formula, Rd R8 independently represents a hydrogen atom or a monovalent organic group having 1 to 2 carbon atoms. The A atom of the organic base towel can be substituted by a fluorine atom]. In the above aspect, the fluorine-containing solvent is an aromatic fluorine compound having 6 to 20 carbon atoms. In the aspect, the composition for the organic thin film transistor insulating layer is 323440 5 201219376, which comprises a fluororesin (c). In one aspect, the fluororesin (c) is at least one gas resin 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);

(3) [wherein, X represents a monovalent organic group having a fluorine atom of 1 to 20, a fluorine atom or a gas atom]

R9

OH (4) [wherein, Rg represents a 1 ky 1 ene. The ruthenium atom in the alkyl group can be replaced 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. 6 323440 s 201219376 «—^1/2 R1-C.R1 "a)a R 丨c—la f

(R) 5-m~^ \ I) (5) [wherein, Ri. Each of R12 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The ruthenium atom in the organic group may be substituted by a fluorine atom. R represents a hydrogen atom or a monovalent organic group having a number of 1 to 20. 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 replaced 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 same 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 an isocyanato group blocked by a blocking agent and an isothiocyanate group blocked by a blocking agent (i so th i ocy ana to) At least one of the groups in the group. In one aspect, the first functional group is a group represented by the formula (6):

R14 7 323440 (6) 201219376 [In the formula, Xa represents an oxygen atom or a sulfur atom and each independently represents 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):

H

An N-C-N (7) [wherein, xb represents an oxygen atom or a sulfur atom. Rls, Rie and the heart respectively 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 comprising: a source electrode, a drain 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 display comprising the aforementioned organic thin film transistor. ‘D Moreover, the present invention provides a display including the above-described members for a display. [Effects of the Invention] 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 it is driven in the atmosphere. [Embodiment] Next, the present invention will be described in more detail. (Composition for Organic Thin Film Oxide Insulation Layer) <Compound (A)> The organic compound of the present invention; the composition of the composition for the 4-membrane transistor insulating layer 323440

S 8 201219376 The compound (A) has a group having a cyclic ether structure. The term "cyclic ether structure" means a structure in which carbon of a cyclic hydrocarbon is replaced by oxygen. The number of atoms forming a ring in the cyclic ether structure is preferably 1 Å 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 i. 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 (4) is polymerized to polymerize the tensile strength of Qensilestrength. f ^ has a cyclically-based group, and is preferably at least i groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2). Among them, the base system shown by the formula is particularly desirable because it provides a good resistance to the reservoir. In the formulae (1) and (2), the valence organic group to the hydrogen atom is simply represented by Rs. The nitrogen atom in the organic group may be substituted by a gas of 0-type carbon ==: a straight-chain, branched, cyclic, or any number of 1 to 20-valent organic groups may be, for example, a chain hydrocarbon group, a carbon number of 3 to a branch of 20; a hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a direct bond hydrocarbon group of ===, a divided tobacco group of Wei 3 to 6, a number of 1 to 6 cyclic hydrocarbon groups, and a carbon number of 6 An aromatic hydrocarbon group of up to 20. The linear hydrocarbon group having a carbon number of 1 to 20, a hydrocarbon group or a cyclic hydrocarbon group having 3 to 20 carbon atoms to 6 is substituted by a fluorine atom. The hydrogen atom contained in the branched group having a carbon number of 3 to 20 may be 323440 9 201219376 The hydrogen atom in the aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted by an alkyl group, a halogen atom or the like. The monovalent organic group having 1 to 20 carbon atoms which may have a substituent, and examples thereof include an anthracenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a third butyl group, and a ring. Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cylcohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthracenyl, fluorenylphenyl, Dimethylphenyl (xylyl), dimerylphenyl (dime1:hylphenyl), tridecylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butyl , methylnaphthyl, dimethylnaphthyl, trimethylnaphthyl, vinylnaphthyl, anthracenyl, ethyl fluorenyl, pentafluorophenyl, trifluorodecyl phenyl, chloro Phenyl, bromophenyl, 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, a group having an oxetane structure, or the like. In the group having an oxetane structure, 'containing a group having a 3-ethyloxetane structure. 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, for example, bis(3, _epoxypropyloxypropyl)-1,1,3,3-tetramethyldiazepine, 3-ethyl~3-(2) ,-ethylhexyloxyindenyl)-oxetane, 3-ethyl-3-{[(3-ethyl-oxetan-3-yl)nonyloxy]indenyl}oxy Heterocyclic butane. <Fluorinated solvent (B)>

10 323440 S 201219376 The fluorine-containing solvent (B) contained in the composition for an organic thin film transistor insulating layer of the present invention is a compound in a composition under the usual environmental conditions used in the production of an organic thin film transistor ( A) An organic compound having a fluorine atom which is fluidizable and volatilizable. When the composition for an organic thin film transistor insulating layer contains the fluorine-containing solvent (B), the composition for the organic thin film transistor insulating layer enhances the wettability and diffusion property when it is 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 particularly lacks 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 fluoride having 6 to 20 carbon atoms. The aromatic fluorine compound having 6 to 20 carbon atoms may, for example, be hexafluorobenzene, pentafluoroindole, octafluoroantimony or tetrafluorobenzal ether. The fluorine-containing solvent (B) may be added with a solvent such as a leveling agent or a surfactant as needed. 11 323440 201219376 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. The local adjustment is. <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 (e.g., 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 which can be bonded to a surface having a high polarity such as a glass surface or a metal surface. Thereby, the adhesion of glass, metal, etc. is improved by the insulating layer containing the resin (C). <Fluororesin (C-1)> An example of a preferred fluororesin (C) is a fluororesin containing a hydroxyl group, for example, a repeating unit represented by the formula (3) and a repeating unit represented by the formula (4) (C-1) ).

12 323440 ^ (3) 201219376

I R9 OH (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 fluorine-containing resin (C-1), R9 represents an alkylene group. The hydrogen atom in the alkylene group may be substituted by a fluorine atom. Examples of the stretching group include, for example, a methylene group, an ethylene group, a propyl group, a butyl group, a hexyl group, and an octyl group. In one aspect of the repeating unit represented by the formula (4), R9 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 13 323 440 201219376, for example, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether. The photopolymerization initiator may, for example, be acet〇phen〇ne, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxyethyl benzene, 4-isopropyl-2-hydroxy-2-methylpropenylbenzene, 2-hydroxy-2-mercaptopropylbenzene, 4,4'-bis(diethylamino)diphenyl ketone, two stupid Benzophenone, (o-benzoyl) benzoic acid methyl ester, phenyl 2-propanedione-2-(o-ethoxycarbonyl) fluorene, phenyl phenyl-1, 2-propene Diketo-2-(o-benzoinyl), benzoin, benzoin decyl 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; a tanning derivative such as hydrazine or hydrazine; a derivative of thiooxanthone such as chlorothioxanthone, 2-methylthiaxanthone or 2-isopropylthioxanthone; diphenyl disulfide, two Sulfur compounds such as dithiocarbamateThe 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-dimercapto valeronitrile), 4,4'-azobis(4-cyanovaleric acid), 1, Γ-azobis(cyclohexane) (1,1'-azobis (cyclohexanecarbonitrile), 2, 2'-azobis(2-methylpropane), 2, 2'-azobis(2-mercaptopropene) (2, 2 An azo compound such as '-azobis(2-methylpropionamidine)) dihydrochloride; decyl ethyl ketone peroxide, decyl isobutyl ketone peroxide, cyclohexanone peroxide, over 14 323440

201219376 Oxidized ketones such as acetoxyacetone; isobutyl peroxide, benzammonium peroxide, 2, 4-dichlorobenzhydryl peroxide, o-methylbenzhydryl peroxide, peroxidation Barium sulfhydryl, peroxydiphenyl fluorenyl peroxide, etc.; 2, 4, 4-trimethylpentyl-2-hydroperoxide, diisopropyl peroxide, rat peroxidation Hydrogen peroxides such as cumene hydroperoxide and tributyl peroxide; dicumyl peroxide, tributyl cumene peroxide, dibutyl butyl peroxide, etc. Dialkyls; tris(tert_butylperoxy) triazine (tris); perylene peroxide, i-di-tert-butylcyclohexane, Oxidized ketals such as 2,2-di-tert-butyl)butane; tert-butyl peroxypivalate, tert-butyl peroxy 2-ethylhexanoate, peroxidation Tert-butyl isobutyrate, di-tert-butyl hexahydrophthalate, di-p-butyl succinate, 3, 5, 5-tridecanoic acid peroxide Tertiary butyl ester, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, hexamethylene peroxide, succinyl dibutoxide, alkyi perester, peroxidation Carbonic acid-soluble esters such as diisopropyl acid-decomposed, dibutyl phthalate dibutyl acrylate, and butyl butyl acrylate. The fluororesin (Ci) 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 raw material which is a repeating unit represented by the formula (4). It is produced by a polymerizable monomer other than a polymerizable monomer. The other polymerizable monomer may, for example, be an unsaturated hydrocarbon and a derivative thereof, a vinyl ether derivative or the like. 15 323440 201219376 The type of other polymerizable monomer is appropriately selected depending on the characteristics required for the insulating layer such as a 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. The unsaturated hydrocarbon and its derivative may, for example, be 1-butene, pentene, 1-hexene, 1-octene, vinylcyclohexane, ethylene chloride or allyl alcohol. The vinyl ether derivative may, for example, be mercapto 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 which is a raw material of the repeating unit represented by the formula (3) is adjusted so that the amount of the gas introduced into the fluororesin (C-1) is an appropriate amount. The fluororesin (C-1) which can be used in the present invention may, for example, be a poly(trifluoroethylene-co-tetra-4-butylbutylethyl bond-co-ethylethylene radical) or a poly(three gas B) Dilute-to-tetramethyl-butyl-ethyl bond-co-butylethyl bond), poly(trifluoroethylene-co-4-tetra-butylbutyl bond-co--3-chloride Nonylphenylethyl ether), poly(trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-cinnamic acid vinyl), 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 repeat represented by the formula (5). The unit further contains two or more first functional groups, and the first functional group is a functional group that generates a second functional group that reacts with active hydrogen by the action of electromagnetic waves or heat. 16 S 323440 201219376 (R)5-m

(5) In the structure of the repeating unit contained in the fluororesin (〇2), the point to the centimeter indicates the hydrogen atom or the carbon number! To the 2G _: price (5) machine base. R represents a hydrogen atom or a monovalent organic group having 1 to 2 carbon atoms. A fluorine atom or a monovalent organic group having a fluorine atom having 1 to 2 carbon atoms. A divalent organic group having a carbon number of 1 to 20 is shown. The hydrogenogen a in the divalent organic group is substituted by a fluorine atom. a represents an integer from 〇 to 20, and m represents 丨 to 5, countable. When Raa is plural, the same may be the same, or the phase $ = the same may be the same 'may be different. When R f is plural, ':, : etc. may be the same' or may be different. &quot; The divalent organic group having 1 to 20 carbon atoms may be a straight chain or a branched one, and may be an aliphatic hydrocarbon, or an aromatic hydrocarbon, or may contain a hetero atom such as an oxygen atom or a sulfur atom. For example, a divalent branched aliphatic hydrocarbon group having a carbon number of 1 to a milky alkal chain aliphatic hydrocarbon group, a carbon number of 3, a mussel straight magnetic number 3 Βλλ, a monovalent cyclic aliphatic hydrocarbon group, or an alkane The carbon substituted by the base is preferably a carbon number Γ to a divalent branch which may have a reduction of 6; an aliphatic tobacco group, a carbon number of 3 to a branched moon, and a divalent carbon number of 3 to 6. Cyclic fat 323440 17 201219376 A hydrocarbon group, a divalent aromatic smoky group having 6 to 20 carbon atoms which may be substituted by an alkyl group or the like, -0-C0-. 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 smoky group which may have a slave number of 6 to 20, and examples thereof include a phenyl group, a naphthyl group, a decyl group, a dimethylphenyl group, a trimethyl phenyl group, and an extended ethyl group. Phenyl, di-extended ethylphenyl, tri-ethylphenyl, propyl-phenyl, butyl-phenyl, methyl-naphthyl, dimethyl-naphthyl-methyl-naphthyl, Vinylnaphfhylene, ethenylnaphthylene, methyl thiol, ethyl thiol and the like. Examples of the monovalent organic group having a carbon number i to 2 Å represented by L to the compound of R, for example, the same ones as those of the monovalent organic group having a carbon number i to 2 Å represented by R1. An example of the valence organic group having a carbon number of the fluorine atom to 2{) shown by Μ is, for example, the same group as the one having a fluorine atom having 1 to 2 g of a fluorine atom. The monovalent organic group having an inverse number i to 2 Å of R, for example, a linear aliphatic ketone having 1 to 2 carbon atoms, a branched aliphatic hydrocarbon having 3 to 20 carbon atoms, and a carbon number of 3 To 2 ) 沾 与 番 番 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 状 芳香族 芳香族 芳香族 芳香族 芳香族The gram is a fatty hydrocarbon group, a carbon number of 3 to 6 hydrocarbon groups, and a carbon number of 6 to 20 (10) hydrocarbon groups. The aliphatic atom 323440 18 201219376 The hydrogen atom in the aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted by an alkyl group, a gas atom, a bromine atom, a moth 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, cyclopentyl, cyclohexynyl, phenyl, naphthyl, anthracenyl, fluorenylphenyl, diphenylphenyl, dinonylphenyl, diterpene Phenylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, butylphenyl, methylnaphthyl, dimethylnaphthyl, trimethylnaphthyl, vinyl Naphthyl, methyl fluorenyl, ethyl fluorenyl, chlorophenyl^ in the form of the repeating unit represented by the formula (5), Ri. When Ru is a nitrogen atom, Rf is a fluorine atom, a is 0, and m is 5. The resin (C_2) which can be used in the present invention contains a repeating unit represented by the formula (5) and contains two or more first functional groups which are formed by the action of heat or heat of electromagnetic waves. A functional group of an active hydrogen counter 2 functional group. ~ The term "active hydrogen" means a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom. The second functional group which is reacted with the active hydrazine is preferably protected (closed) before being heated in the forming step. ^ = The first functional group is preferably deprotected by heat and generates the second official of the disk. This is because the storage stability of the composition can be improved, and the first B-group can be, for example, an isothiocyanate group blocked by a blocking agent and blocked by a blocking agent. &quot; soil, or 323440 19 201219376 The aforementioned isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent, by allowing the blocking agent 1 molecule to have only one isocyanate group or A blocking agent of an active hydrogen reacting with an isothiocyanate group is produced by reacting with an isocyanate 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 compound, an active sulfhydryl 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 ° ratio compound, and 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 fatty compound and a D-based oxime compound. Hereinafter, a specific blocking agent will be exemplified. The alcohol-based compound may, for example, be decyl alcohol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl acesulfame, methyl carbi to 1 ), benzoquinone, cyclohexanol, and the like. The compound which may be mentioned is, for example, expectant, indophenol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoate or the like. The active fluorenylene-based compound may, for example, be dimethyl malonate, diethyl malonate, decyl acetate, ethyl acetate or acetacetone. The thiol compound may, for example, be butyl mercaptan or dodecyl mercaptan. Examples of the guanamine-based compound include acetani ide, acetamide, ε-caprolactam, (5-valeroinamide, τ-butylidene, etc., and the quinone imine compound can be used. For example, dinodiimine, cis-butyl 20 323440 ^ 201219376 ene diimine, etc., an imidazole compound, etc. The urea-based compound may, for example, be urea, :::, 2: fluorenyl; Examples of the monthly-deficient compound include methyl ethyl urea (__〇, methyl ethyl ketone, B-, propylene, such as diphenylamine, aniline, or the like. The amine compound can be I ( y Ereimine), polyethylenimine, etc. The bisulfite salt may, for example, be sodium bisulfite. For example, the Xenopus compound may be, for example, 2-hydroxy=2-substrate-specific; σ 比 唑 azole, 3, 5-diethylpyrazole, etc. The sap can be blocked by the __, the base shown by = (8) and Xa is the base of the oxygen atom, the formula (7) And the base of the oxygen atom. The blocked iso-sulphuric acid earth used in the present invention is preferably a group represented by the formula (6) and a group of a Xa $ sulfur atom, a group represented by the formula and Xb is a group of a sulfur atom.

u Xb N Η 谷 a R13 - n - S - n 〆 ~ NC-0 - n = = ^ R14 * &gt; 17 (6) (7) In the formula (6), Xa represents an oxygen atom or a sulfur atom, Rii independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having a carbon number of 1 to 20 represented by Ri4 and Ri, for example, and Ri may be mentioned. The same group as the monovalent organic group shown by Ri2. In one aspect of the repeating unit represented by the formula (6), Xa is an oxygen atom, Rl3 is a methyl group, and R14 is an ethyl group. 323440 21 201219376 In the formula (7), Xb represents an oxygen atom or a sulfur atom, and Rls, Rle and Ri7 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 Ris, Rie and Rn include, for example, the same groups as those of the monovalent organic group represented by Rio to Rn. In one aspect of the repeating unit represented by the formula (7), Xb is an oxygen atom, and Rl5 to Rl7 are a hydrogen atom. The isocyanato group blocked by the blocking agent may, for example, be a fluorene-(methyleneamino) ruthenylamino group (0-(11161:11711(171163111111〇)〇81'13〇乂7311^11〇), 0 -(1-ethylideneamino)carboxyamino, 0-(1-methylethylideneamino)alkyl, 〇-[1-decyl propyleneamino]carboxyamino, N-3, 5-dimercaptopyranyl)amino, (N-3-ethyl-5-mercaptopyrazolylcarbonyl)amino, (n_3, 5_ethylidene) Amino group, (N-3-propyl-5-fluorenyl π is more than α-based) amine group, (Ν-3-ethyl-5-propyl η-pyrazolylcarbonyl)amino group The isothiocyanate group blocked by the blocking agent may, for example, be 〇((methyleneamino)thiomethylamino group, 0-(1-ethylideneamino)thiolamino group, 〇__ (1-methylethylamino)thiocarboxyamino, 〇-[1-mercaptopropylamino]thioheptylamino, (Ν-3,5-dimercaptopyrazylthiocarbonyl) Amino group, (Ν_3_ethyl_5_methyl alpha ratio 0 thiophene tetamine) amine group, (Ν-3, 5-diethyl η ratio β thiol group) amine group, (Ν- 3-propyl-5-fluorenyl ratio β-based thiocarbonyl)amine, (Ν-3-ethyl-5- The first functional group used in the present invention is preferably an isocyanate group blocked by a blocking agent. Next, the production of the fluororesin (C-2) used in the present invention will be described. The chaotic resin (C-2) can be produced, for example, by a polymerizable monomer which is a raw material of a repeating unit represented by the formula (5) 323440 22 201219376 and a polymerizable property containing a first functional group. A method of copolymerizing a monomer using a photopolymerization initiator or a thermal polymerization initiator. The photopolymerization initiator and the thermal polymerization initiator may, for example, be used in the production of the fluororesin (C-1). The same photopolymerization initiator and thermal polymerization initiator. The polymerizable monomer which is a raw material of the repeating unit represented by the formula (5) may, for example, be 2-trifluorodecylstyrene or 3-trifluoromethyl. Styrene, 4-trifluoromethylstyrene, 2,3,4,5,6-pentafluorostyrene, 4-fluorodecylstyrene, etc. The polymerizable monomer containing the first functional group can be exemplified Such as having an isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturatedly bonded monomer. An isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturatedly bonded monomer can be obtained by having 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 - mercapto-eneoxyethyl isocyanate, 2-(2'-mercaptopropenyloxyethyl) oxyethyl isocyanate, etc. A compound having an unsaturated double bond and an isothiocyanate group, for example, 2-propenyloxyethyl isothiocyanate, 2-methylpropenyloxyethyl isothiocyanate, 2-(2'-mercaptopropenyloxyethyl)oxyethyl isosulfide Cyanate esters, etc. 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. 23 323440 201219376 The aforementioned monomer having an unsaturated double bond and an isocyanate group blocked by a blocking agent, for example, 2-[0-[1 '-mercaptopropylamino]carboxyamino group of methacrylic acid] Ethyl ester, 2-[Ν-[Γ,3'-dimercaptopyrazolyl]carboxyamino]ethyl methacrylate, 2-[0-[Γ-mercaptopropylamino] methacrylate Thiocarboxyamino]ethyl ester, 2-[Ν-[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, mercapto acrylates 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, di-stere esters of fumaric acid and their derivatives, cis-butane a dialkyl ester of a maleic acid and a derivative thereof, a dico-ester of methylene succinic acid and a derivative thereof, an N-vinylamine derivative of an organic acid retardation, and a butene 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 the adhesion to the adjacent faces of the insulating layer such as the gate electrode and the surface of the substrate, it is selected such as decyl acrylate and its derivative 24 323440

S 201219376 A monomer that imparts flexibility, such as acrylic acid vinegar and its derivatives. In a preferred embodiment, a monomer having no active ruthenium-containing group such as an alkyl (mercapto) acrylate such as a mercapto 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 can be used, and although the amount used may be limited, a polyfunctional acrylate may also be used, and for example, bismuth acrylate hydrate, acrylic acid, and acrylic acid may be used. Propylene vinegar, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, dibutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, acrylic acid Cyclohexyl ester, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl ethyl acrylate, Ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trishydroxypropyl propane diacrylate, trihydroxyl Mercaptopropane triacrylate, pentaerythritol pentaacrylate, N,N-dimercaptopropenylamine, N,N-diethylpropenylamine, N-propenylmorphomorpholine (N- Acryloylmorpholine), 2, 2, 2-trifluoroacrylate Ethyl ester, propionate 2, 2, 3, 3, 3-pentafluoropropyl ester, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-propene (Perfluorohexyl)ethyl ester, 25 323440 201219376 3-perfluorohexyl 2-hydroxypropyl acrylate, 2-(perfluorooctyl)acetic acid acrylate 3-perfluorooctyl-2-propyl propyl ester, C Capric acid (perfluorodecyl) acetamidine, 2-(perfluoro-3-mercaptobutyl)ethyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 2-(perfluoro) 5_mercaptohexyl) ethyl ester, 2-(perfluoro-3-mercaptobutyl) 2 -hydroxypropyl acrylate, 3 (perfluoro-5-methylhexyl) 2 -hydroxypropyl acrylate, 2 - (perfluoro) Methyl octyl)ethyl ester, 3-(perfluoro 7-methyloctyl)-2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate , 1H, 1H, 7H-dodecafluorobutyr, 1H, 1H 9H_hexadecene, propylene, 1H-1-(trifluoromethyl)trifluoroethyl ester, 1 acrylate , η, hexafluorobutyl ester, and the like. A monofunctional methacrylate can be used for the mercapto acrylate and its derivative, and a polyfunctional mercapto acrylate can also be used although it is limited in use, and examples thereof include decyl methacrylate and methacrylic acid B. 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, phenyl methacrylate, 2-hydroxy propyl methacrylate Ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenyl ethyl methacrylate, ethylene glycol dimercapto acrylate, propylene glycol Dimercapto acrylate, L4_butanediol dimethacrylate, diethylene glycol dimercapto acrylate, triethylene glycol dimethacrylate, trishydroxypropyl propane dimercapto acrylate, trihydroxyl Methyl propane 323440 ^ 26 201219376 III Mercapto acrylate, neopentyl alcohol penta methacrylate, N,N-dimercapto fluorenyl decylamine, N,N-diethyl decyl acrylamide, N-methyl propylene fluorenyl Lin, 2,2,2-trifluoroethyl methacrylate, 2'2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, fluorenyl 3-Perfluorobutyl-2-hydroxypropyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluoro) methacrylate Octyl)ethyl vinegar, 3-perfluorooctyl-2-propylpropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methyl butyl methacrylate Ethyl ester, 3-(perfluoro-3-mercaptobutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 2-(methacrylic acid) Perfluoro-3-mercaptobutyl)-2-hydroxypropyl ester, 3-(perfluoro-5-mercaptohexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro 7-fluorenyl methacrylate) Ethyl ester, 3-(perfluoro 7-methyloctyl)-2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, methyl propyl methacrylate Acid 111,111,511-octafluoropentyl ester, 111,111,711-dodecyl butyl methacrylate, 1H, 1H, 9H-hexadecafluorodecyl methacrylate, 1H-1-methacrylate Trifluorodecyl)trifluoroethyl ester, methacrylic acid 1H, 1H, 3H-hexafluorobutyl ester, and the like. Styrene and its derivatives, for example, styrene, o-decyl styrene, m-decyl styrene, p-nonyl styrene, 2, 4-dimercaptostyrene, 2, 5-dimethyl styrene , 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimercaptostyrene, 2,4,6-trimethylstyrene, 2, 4, 5-three Mercaptostyrene, pentadecyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromo styrene, Bromostyrene, p-bromostyrene, o-methoxystyrene, 27 323440 201219376 m-decyloxystyrene, p-nonyloxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- Vinyl biphenyl, 3-vinyl biphenyl, 4-vinyl biphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-vinyl-p-terphenyl, 1-vinyl anthracene, α- Nonylstyrene, o-isopropenylfluorene, m-isopropenyltoluene, p-isopropyl-decyltoluene, 2,4-dimethyl-α-mercaptostyrene, 2,3-dimethylmethylbenzene Ethylene, 3, 5-dimercaptophenylene oxide, diopside Yl - α- Yue phenyl ethylene, α - ethylstyrene, chlorostyrene, divinylbenzene, divinyl biphenyl, diisopropylbenzene, styrene 4_ group. Examples of the acrylonitrile and derivatives thereof include acrylonitrile and the like. Examples of the methacrylonitrile and derivatives thereof include mercaptoacrylonitrile. The vinyl ester of an organic carboxylic acid and a derivative thereof may, for example, be ethyl 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 isopropyl acetate, allyl benzoate, diallyl adipate, diisopropyl acetonate or diene isophthalate. Propyl ester, phthalic acid diene phthalate and the like. The dialkyl ester of fumaric acid and derivatives thereof may, for example, be dimethyl dibutanoate, diethyl fumarate, diisopropyl fumarate or fumaric acid. 2 second butyl ester, diisobutyl methacrylate, antibutanic acid, n-butyl butyl, anti-butyric acid, 2-ethylhexanyl, dibutyl benzoate, etc. . The dialkyl ester of maleic acid and derivatives thereof may, for example, be dimethyl dimethyl succinate, diethyl maleate, diisopropyl acrylate, cis 323440 28 201219376 Dialkyl enediate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, diphenyl maleate Deliberate and so on. The dialkyl ester of sulfhydryl succinic acid and derivatives thereof may, for example, be decyl succinate, dimethylene succinate, diisopropyl succinic acid, or isopropyl Dimethyl succinic acid dibutyl acrylate, diisobutyl sulfonium succinate, di-n-butyl sulfenyl succinate, di-2-ethylhexyl methylene succinate, sulfhydryl Diphenyl succinate and the like. The N-vinylamine derivative of the organic carboxylic acid may, for example, be N-fluorenyl-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-octyl, vinylcyclohexane, acetonitrile, allyl alcohol or the like. The organic ruthenium compound containing an unsaturated bond may, for example, be a propyl trimethyl hydrazine, an allyl triethyl hydrazine, an allyl tributyl fluorene, a tridecyl vinyl fluorene or a triethyl vinyl fluorene. Wait. Among these, acrylonitrile-based styrene, acrylonitrile, mercapto acrylonitrile, and allyl tridecyl fluorene are 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 exceeds 60% by mass, the compatibility with the fluorine-containing solvent (B) is deteriorated, and the preparation of the composition becomes difficult. 29 323440 201219376 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) &lt;is either linear, branched or cyclic. <Cationic polymerization initiator> It is preferred to further add a photocationic polymerization initiator or a thermal cationic polymerization initiator to the composition for an organic thin film transistor insulating layer of the present invention. 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 salt. The onium salt may, for example, be diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate or decylphenylpyridinium tetrakis(pentafluorophenyl)borate. The salt-salting may, for example, be triphenylphosphoric acid, hexafluorophosphoric acid (phenylthio)phenyldiphenylphosphonium, hexafluoroantimonate triphenyl and hexafluoroantimonic acid (phenylthio)phenyldiphenyl. Bismuth, bis(hexafluorocyclohexylic acid) 4,4'-bis[bis(/3-hydrylethoxy)phenylindenyl]phenyl sulfide, hexafluoro-acid 4-[4-(4-third Butylbenzhydryl)phenylthio]phenylbis(4-mercaptophenyl)anthracene. Specifically, the photocationic polymerization initiator may be, for example, a trade name of Rhodorsi 1 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 Co., Ltd.), trade name ADEKA OPTOMER-SP-170 (made by Adeka Co., Ltd.), brand name ADEKA OPTOMER-SP-172 (made by Adeka Co., Ltd.), etc. 323440 g 30 201219376 Further, a salt-transfer compound described in JP-A-9-118663 can also be used. Specifically, the thermal cationic polymerization initiator may, for example, be a trade name: ADEKA 0ΡΤ0Ν-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 1 化合物 when the compound (A) having a group having a cyclic ether structure is 1 〇 In the case of 〇 by weight, it is more preferably 0.0001 to 30 parts by weight of the range of 0.001 to 10 parts by weight. Further, the photocationic polymerization initiator or the thermal cation-incorporated kinetic initiator may be used alone or in combination of two or more compounds (A) having a cyclic structure, a fluorine-containing solvent (B), and The fluororesin (C) as needed is mixed with a cationic polymerization initiator or the like to obtain a composition for an organic thin film transistor insulating layer of the present invention. When the fluororesin (C) is contained in the composition for an organic thin film electric insulating layer of the present invention, the content thereof is preferably 6 〇 0 parts by weight or less based on the weight of the compound (A). It is from 1 to 500 parts by weight. The organic thin film transistor insulating layer is used in the fluororesin (C) in the polymer film insulating layer, and if the phase is more than 600 parts by weight based on the weight of the compound (A), the organic thin film transistor insulating layer The solvent resistance is lowered. When the fluororesin (C-1) having a hydroxyl group is used as the fluororesin (C), the total amount of the fluororesin (C-1) in the composition for an organic thin tantalum oxide insulating layer of the present invention is relative to the compound ( A) In terms of 100 parts by weight, it is 50 to 600 parts by weight, preferably 丨〇〇 to 500 parts by weight, more desirably 200 to 400 parts by weight. 31 323440 201219376 The content of the fluororesin (c-1) in the composition for the organic thin film transistor insulating layer is caused by less than 5 parts by weight relative to the weight of the compound (A). When the aggregation of the coating film exceeds 6 parts by weight, the solvent resistance of the organic thin film transistor insulating layer is lowered. Further, the content of the fluorine-containing solvent (B) in the composition for the organic thin film transistor insulating layer at this time is 100 to 3000 parts by weight with respect to 1 part by weight of the compound (A). 〇〇 to 2 parts by weight, more desirably 800 to 1500 parts by weight. The content of the fluorine-containing solvent (β) in the composition for the organic 4-membrane transistor insulating layer is 'flat with respect to the weight of the compound (Α) ι, if less than 1 part by weight, the coating film is flat The property is lowered, and when it exceeds 3 parts by weight, the organic thin film transistor insulating layer may generate a hole. The fluororesin (C) can also be used by mixing a fluororesin (〇1) having a hydroxyl group and a fluororesin 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 iridium oxide insulating layer, polarization of the insulating layer is suppressed and resistance is caused. The solvent is high. 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, and a composition for an organic thin film transistor gate insulating layer used for forming a gate insulating layer. Object. The composition for an organic thin film transistor insulating layer is preferably a protective layer for forming an organic thin film transistor. 32 323440 201219376 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 reed 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 dummy 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 &amp; and the electrodeless electrode 6, the organic 323440 33 201219376 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 idle bottom contact type organic thin film transistor can be manufactured, for example, by forming a gate electrode on a substrate, forming a gate insulating layer on the gate electrode, and forming a source electrode on the gate insulating layer. , a drain electrode, a source electrode, and a drain electrode form an organic semiconductor layer, and then a protective insulating layer is formed. 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, drying and curing. 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, ink jet 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 plate of a resin and a plastic, a film, a glass plate, a fascia, or the like. The material of the electrode is formed by a conventional method such as a steaming method, a sputtering method, a printing method, or an inkjet printing method using chromium, gold, silver, or the like. As the organic semiconductor compound, a 7-inch conjugated polymer is widely used, and for example, polypyrrole, polythiophene, polyaniline, polyallylamine, fluorene, polycarbazole, polyindene (polyind) can be used. 〇le), 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 tetrathiol 34. 323440 g 201219376 wattene ^: rathiafulvalene) derivative, tetrazinyl quinone derivative, fullerene, carbon nanotubes. Specifically, for example, a condensate of 9,9-di-n-octyl fluorene-2,7-di(ethyl borate) and 5,5,-dibromo-2,2'- hydrazine can be exemplified. 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 ordinary pressure to 2 〇〇c&gt;c. The solvent may, for example, be chloroform, methyl bromide, anisole, 2-glyoxime or propylene glycol monoterpenoid 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. 1. 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. The display member having the organic thin film transistor can be suitably used to produce a display having a member for display. [Examples] &lt;The present invention is described below by way of examples, but the invention is not limited to the examples. Synthesis Example 1 (Synthesis of Polymer Compound 1) 2,7-bis(1,3,2-dioxaborolane 2)-9,9-octyl group (2) was mixed under an inert gas atmosphere. , 7-bis(l,3,2-dioxaborolan -2-yl)-9, 9-dioctylf luorene)5. 20 g, bis(4-bromophenyl)_(4_ 323440 35 201219376 second butylphenyl 4.50 g of an amine, 2 mg of palladium acetate, 15.1 mg of tris(2-nonylphenyl)phosphine, ammonium decyltrioctyl ammonium chloride (manufactured by Mdrich, trade name "Aliquat 336" (registered trademark)) 〇. 9 lg, 7 ml of toluene, heated to · 105 C. To the reaction solution, a 19-liter 2 mol/kg sodium carbonate aqueous solution was dropped to reflux for 4 hours, and then stearic acid 121 was added thereto, followed by reflux for 3 hours. Then, an aqueous solution of sodium sulphate diethyldithiocarbamate was added, and washed 3 times with 8 wt% acetic acid aqueous solution at 8 〇β (: stirring for 4 hours, after cooling (in water W) ml). The mixture was washed three times, washed three times with water (60 ml), and purified by oxidizing the column and the column. The obtained f-benzene solution was added dropwise to methanol (3 liter), and after stirring for 3 hours, the obtained solid was filtered and dried. The yield of the obtained polymer compound oxime represented by the following formula was 5.25 g. Here, η in the following formula represents the degree of polymerization.

2x1 〇5。 The weight average molecular weight of the polymer compound 1 is 2. 6x1 〇5. The measurement conditions of the weight average molecular weight were as follows: GPC' column of Shimadzu: "Tskgel superHM-H" l + "Tskgel super 0", and mobile phase: THF. 323440 g 36 201219376 Synthesis Example 2 (Synthesis of Polymer Compound 2) Azobis(2-methylpropionitrile) 0. 〇lg, 2, 3, 4, 5, 6_pentafluoropyrene (made by Wako Pure Chemical Industries, Ltd.) 3. 00g was placed in a 50 ml pressure-resistant container (manufactured by ACE), and after bubbling with argon, the plug was tightly sealed and polymerized in an oil bath at 60 ° C for 24 hours to obtain a polymer compound 2 represented by the following formula. 2, 3, 4, 5, 6-pentafluoroindole solution. Here, η in the following formula represents the degree of polymerization.

The polymer compound 2 obtained from the polymer compound 2 had a weight average molecular weight of 88,000 from a standard polystyrene. 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 Insulator Layer) In a 20 ml sample vial, '40% by weight of "Lumif Ion (registered trademark) LF200F" was placed (made by Asahi Glass Co., Ltd., H price was 45 mg K0H/ g) 2, 3, 4, 5, 6-pentafluorotoluene solution 2. 0〇g, "ARONE 0XETANEC registered trademark" OXT-221" (made by East Asian Synthetic) 〇.27g, "Rhodorsi 1 (registered trademark) 2074 (Rhodia Japan) 0· 〇〇〇 54g, 2, 3, 4, 5, 6-pentaoxy 323440 37 201219376 Benzene solution (manufactured by Wako Pure Chemical Industries, Ltd.) 2. 00g, mixed to prepare a solution. The resulting solution was filtered through a membrane filter having a pore size of 0.45 # m to prepare a composition 1 for an organic thin film transistor insulating layer. "AR0NE 0 (registered trademark) 0XT-221" is a compound having the following structure.

"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), R4 represents a stretching group.

(2 - a) (3 - a) (Production of the field-effect type organic thin film transistor) The polymer compound 1 was dissolved in diphenylbenzene to prepare a solution having a concentration of 0.5% by weight (organic semiconductor composition), This solution was filtered through a membrane filter having a pore size of 0.45 # m 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 spin coating 38 323440 g 201219376, and dried at 200 ° C for 1 minute in nitrogen. Forming an active layer of about (10) (10) thickness. Then, on the obtained active layer, the composition film b for the organic thin film transistor insulating layer was applied by spin coating, and then dried at 5 ° C for 5 minutes, and a UV/ozone purifier was used in argon gas (Model UV-1, manufactured by SAMC0) was irradiated with ultraviolet rays (254 nm) for 1 minute. Then, at 1〇0. (: calcination for 30 minutes to form a protective insulating layer having a thickness of about 4 / im, and a field effect type organic thin film transistor 1 was produced. <Optocrystalline characteristics> For the field effect type organic thin film transistor 1 produced, electricity was measured in the atmosphere. Crystal characteristics: Vacuum probe (BCT22MDC-5-HT-SCU; long 濑) for the condition that the gate voltage Vg is in the range of 20 to -40 V and the source-to-electrode voltage Vsd is varied from 0 to -40 V. The electronic device was measured in the atmosphere. The measured threshold voltage (yth) is shown in Table 2. Comparative Example 1 (Production of Field Effect Organic Thin Film Transistor) Except for 2 in Polymer Compound 2 , 3, 4, 5, 6-pentafluoromethyl stupid solution 1.0 (^ added 2,3,4,5,6-pentafluoroantimony solution 1〇〇§ and a film with pores and 0·45 // m In the same manner as in the first embodiment, a field effect type organic thin film transistor was produced in the same manner as in the first embodiment, except that the composition for the organic thin film transistor insulating layer was replaced by the composition 2 of the organic thin germanium dielectric layer prepared by the filter. The characteristics of the transistor are measured in x gas. The thickness of the protective insulating layer is about 6 and the absolute value of the voltage is 40V or more, so that the gate is electrically A bar that is pressed to 1 and causes the source-drain voltage Vsd to vary from 〇 to _4〇v cannot be driven. ^ * 323440 39 201219376 [Table 1] Vth Example 1 -9. 0V Comparative Example 1 [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing the structure of a bottom gate contact type organic thin film transistor according to an embodiment of the present invention. Fig. 2 is a view showing another embodiment of the present invention. Schematic diagram of the structure of the gate bottom contact type organic thin film transistor. [Main component symbol description] 1 substrate 2 gate electrode 3 gate insulating layer 4 organic semiconductor layer 5 source electrode 6 drain electrode 7 protective layer 40 323440

Claims (1)

201219376 VII. Patent application scope: A composition for an organic thin film transistor insulating layer comprising: a compound (A) having a group having a ring-shaped structure, and a fluorine-containing solvent (β). 2. The composition for an organic thin film transistor insulating layer according to the above aspect of the invention, wherein the group having a cyclic ether structure is selected from the group represented by the formula and the group represented by the formula (2). At least one base in the group; [wherein, Ri to R3 each independently represent a hydrogen atom or a valent organic group having 1 to 2 carbon atoms; a hydrogen atom in the organic group may be substituted by a fluorine atom] P_ O (2) Fluorine compound. [wherein R4 to Rs each independently represent a hydrogen atom or a monovalent organic group having a carbon number of 丨 to 2〇; a hydrogen atom in the organic group may be substituted by a fluorine atom]. The composition for an organic thin film transistor insulating layer according to claim 1 or 2, wherein the fluorine-containing solvent is an aromatic having a carbon number of 6 to 20. 4. For example, the item (4) items 1 to 3 + A composition for an organic thin film transistor insulating layer according to the rhyme, comprising a fluororesin (c). 5. The organic thin film transistor insulating layer described in Patent Application No. 4 323440 1 201219376 One fluororesin is less; the fluororesin (C) is a fluorobarrier resin (C-1) selected from the following: a fluororesin containing a repeating unit represented by the formula (3); a bismuth resin (C-2) In the group to: containing the repeating unit represented by formula (3) and formula (4) (3) [wherein X represents a monovalent organic group having a carbon number i i 2〇 of a fluorine atom, a fluorine atom or a gas atom] «9 OH (4) [wherein R9 represents an alkylene group; a hydrogen atom in the alkylene group may be substituted by a fluorine atom] fluororesin (C-2): a repeating unit represented by the formula (5) And a fluororesin containing two or more first functional groups, wherein the first functional group is a functional group that generates a second functional group that reacts with active hydrogen by the action of electromagnetic waves or heat; 2 323440 S 201219376 R10 R11 (R) 5m~^J (5) [In the formula 'R!. To R!2 each independently represents 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 carbon number of 1 a monovalent organic group to 20; Rf represents a fluorine atom or a monovalent organic group having 1 to 2 carbon atoms of a fluorine atom; Raa represents a divalent organic group having 1 to 20 carbon atoms; and hydrogen in the divalent organic group The atom may be substituted by a fluorine atom; a represents an integer of 〇 to 2〇, 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 The same may be different; when Rf is plural, the same may be the same or different]. 6. The composition for an organic thin film transistor insulating layer according to claim 5, wherein the 'first functional group is an isocyanate group (iSOCyanat) selected from a blocking agent and is blocked. At least one group of the group of isothiocyanato blocked by a blocking agent. 7. The composition for an organic thin film transistor insulating layer according to claim 5, wherein the first functional group is a group represented by the formula (6); 3 323440 201219376 H ia household 13 —N—COMs/ ^14 (6) === Atomic; a separate monovalent organic base sighing to 20]. The organic thin film transistor insulating layer H t according to item 5 is the group represented by the formula (7); - Ι ί - δ R - '17 16 (7) = the middle two Xb represents an oxygen atom or sulfur Atom; Ri5, Ri6, and ^ are each a residual atom or a valence organic group having a carbon number of 1 to 2 Å. An organic thin film transistor comprising: a source electrode = an organic semiconductor layer; and an insulating layer formed using the organic thin film composition according to any one of the claims. The organic thin film transistor according to claim 9, wherein the insulating layer is an overcoat insulating layer. 11. A member for display, comprising: the organic thin film transistor according to the above patent scope. 12. A display comprising: a member for a demonstrator. ^The scope of the patent range item n 323440 g