TW201246553A - Insulate layer material for light and heat energy cross-linking organic thin film transistor - Google Patents

Abstract

The present invention provides an insulating layer material for organic thin film transistor capable of producing an organic thin film transistor with low absolute value of threshold voltage and less hysteresis. The insulating layer material for organic thin film transistor contains a high molecular compound (A) having a repeating unit containing a substituted maleimide and a repeating unit containing a first functional group, and the first functional group forming a second functional group capable of reacting with an active hydrogen by electromagnetic wave radiation or by heat.

Description

201246553 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a material suitable for forming an insulating layer having an organic thin film transistor. [Prior Art] The organic thin film transistor can be manufactured at a lower temperature than the inorganic semiconductor, so that the substrate can be a plastic substrate or a thin film, and the substrate can be made more flexible than the inorganic semiconductor. Lightweight and not easily damaged components are available. Further, it is also possible to fabricate a device by coating or printing a solution containing an organic material, and it is also possible to manufacture a large number of components at a low cost on a large-area substrate. Further, since the materials for reviewing the crystal crystals are abundant, when used for reviewing materials having different molecular structures, it is possible to manufacture devices having a wide range of property variability. In an electric field effect type organic thin film transistor of an organic thin film transistor, a voltage applied to a gate electrode acts on a semiconductor layer through a gate insulating layer, and controls opening and closing of a drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer. Further, the organic semiconductor compound used in the production of the electric field effect type organic thin film transistor is susceptible to environmental influences such as humidity and oxygen, and the crystal characteristics are liable to deteriorate over time due to humidity, oxygen, and the like. Therefore, in the structure of the bottom gate type organic thin film transistor in which the organic semiconductor compound is exposed, it is necessary to form an overcoat layer covering the entire structure of the element and to protect the organic semiconductor compound from contact with the outside air. 323899 3 201246553 On the other hand, in the structure of the top gate type organic thin film transistor element, the organic semiconductor compound is protected by the gate insulating layer. As described above, in the organic thin film transistor, an insulating layer material is used in order to form a coating layer and a gate insulating layer covering the organic semiconductor layer. In the specification of the present invention, an insulating layer or an insulating film of an organic thin film transistor such as the outer coating layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer. Further, a material used in forming an organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material. Further, the concept of the material referred to herein includes a polymer compound, a composition containing a polymer compound, a resin, and an amorphous material such as a resin composition. In the organic thin film transistor insulating layer material, it is required to have insulation properties and excellent dielectric breakdown strength as a film. Further, in particular, in the bottom gate type electric field effect transistor, the semiconductor layer is formed by being superposed on the gate insulating layer. Therefore, in the organic thin film transistor gate insulating layer material, affinity with an organic semiconductor is required to form an interface with the organic semiconductor, and an organic semiconductor layer of a film formed of the organic thin film transistor gate insulating material The side surface should be flat. In response to such a technique, Patent Document 1 discloses that an epoxy resin and a decane coupling agent are used in combination as an organic thin film transistor gate insulating layer material. In this technique, a base formed by a hardening reaction of an epoxy resin is reacted with a decane coupling agent. This is because the aforementioned hydroxyl groups increase the hygroscopicity of the gate insulating layer material and impair the stability of the transistor performance. Non-Patent Document 1 discloses that a resin which thermally crosslinks a polyvinyl phenol and a melamine compound is used for a gate insulating layer. In this technique, melamine 323899 4 8 201246553 is crosslinked, thereby removing the hydroxyl groups contained in the polyethylene test while increasing the film strength. The pentacene TFT having the gate insulating layer has a small hysteresis, showing durability against gate bias stress. Non-Patent Document 2 discloses that a copolymer of polyvinyl phenol and a copolymer of vinyl phenol and decyl decyl acrylate is used for the gate insulating layer. In this technique, the hydroxyl group of the 'vinylphenol interacts with the carbonyl group of methyl methacrylate to lower the polarity of the film as a whole. The pentacene TFT having the gate insulating layer has a small hysteresis phenomenon and exhibits electrical characteristics of stability. [Prior Art Document] (Patent Document) Patent Document 1: JP-A-2007-305950 C Non-Patent Document) Non-Patent Document 1: Appl. Phys丄ett. 89, 093507 (2006) Non-Patent Document 2: Appl. Phys丄Ett. 92, 183306 (2008) [Problems to be Solved by the Invention] However, when practical use of a light-emitting element such as an organic electroluminescence device (organic EL device) is considered, the operation accuracy of the organic thin film transistor is considered. Further, it is necessary to further improve the absolute value of the threshold voltage (Vth) and the hysteresis of the organic thin film transistor having the gate insulating layer. SUMMARY OF THE INVENTION An object of the present invention is to provide an organic thin film transistor insulating layer material which can produce an organic thin film transistor having an absolute value of a threshold voltage and a small hysteresis. (Means for Solving the Problem) 323899 5 201246553 Various reviews have been made in view of the above circumstances. As a result, it has been found that a gate insulating layer is formed using a specific resin composition capable of forming a crosslinked structure, whereby the threshold voltage of the organic thin film transistor can be made ( Vth) The absolute value and hysteresis are small' to complete the present invention. That is, the present invention provides an organic thin film transistor insulating layer material comprising a polymer compound (A) having a repeating unit represented by the formula (1) and a repeating unit having an i-th functional group. 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.

(1) [wherein R2 represents a hydrogen atom or a methyl group. R3 and R4 each independently represent a one-valent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. The carbon atom in R3 can be bonded to the carbon atom in r4 to form a 5-member or 6-membered ring. Rbb represents a main chain and a side bond of a polymer compound, and a linking moiety 1 having a gas atom represents an integer of Q or ]]. In one embodiment, the polymer compound (A) has a repeating unit represented by the formula (2) 323899 8 6 201246553.

H2

(^aa)u

(R) 5-b (2) [wherein R! represents a hydrogen atom or a methyl group. R represents a hydrogen atom or a one-valent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a one-valent organic group having 1 to 20 carbon atoms having a fluorine atom. Raa represents a main chain and a side chain which are linked to a polymer compound, and may have a linking moiety of a fluorine atom. u represents an integer of 0 or 1, and b represents an integer of 1 to 5. When R is plural, the terms may be the same or different. When Rf is plural, the terms may be the same or different]. In one embodiment, the first functional group is formed from an isocyanato group blocked by a blocking agent and an isothiocyanato blocked by a blocking agent. At least one base selected by the group. In one embodiment, the isocyanate group blocked by the blocking agent and the group represented by the isothiocyanato group (3) blocked by the blocking agent.

(3) [wherein, Xa represents an oxygen atom or a sulfur atom, and R5 and R6 are the same or different, and Table 323899 7 201246553 shows a hydrogen atom or a carbon number of 1 to 20 one-valent organic group]. In one embodiment, the isocyanate group blocked by the blocking agent and the group represented by the isothiocyana group (4) blocked by the blocking agent; η , N^rR7

—N—C—N rC R8 (4) wherein Xb represents an oxygen atom or a sulfur atom, and 117 to R9 are the same or different and represent a hydrogen atom or a one-carbon organic group having 1 to 20 carbon atoms. In one embodiment, the polymer compound (A) contains two or more structural units having one active hydrogen or a structural unit having two or more active hydrogens. Furthermore, the present invention provides the organic thin film transistor insulating layer material comprising an active hydrogen compound having a low molecular compound having two or more active hydrogens, and an active hydrogen compound having two or more active polymer compounds. At least one active hydrogen compound selected in the group. Furthermore, the present invention provides a method of forming an organic thin film transistor insulating layer, comprising: a step of coating a liquid containing the organic thin film transistor insulating layer material on a substrate* to form a coating layer on the substrate And a step of irradiating the coating layer with an electromagnetic wave or an electron beam. In addition, the present invention provides a method of forming an organic thin film transistor insulating layer, comprising: 323899 8 8 201246553 coating a liquid containing the above organic thin film transistor insulating layer material on a substrate, and forming a coating on the substrate a step of laminating; a step of irradiating the coating layer with an electromagnetic wave or an electron beam; and a step of applying heat to the coating layer. In one aspect, the electromagnetic wave is ultraviolet light. Further, the present invention provides an organic thin film transistor having an organic thin film transistor insulating layer formed using the above organic thin film transistor insulating layer material. In one form, the organic thin film transistor insulating layer is a gate insulating layer. Further, the present invention provides a member for a display comprising the above-described organic thin film transistor. Further, the present invention provides a display comprising the above-described member for a display. (Effects of the Invention) An organic thin film transistor having an insulating layer formed using the organic thin film transistor insulating layer material of the present invention has a small absolute value of threshold voltage and a small hysteresis. [Embodiment] In the present specification, "polymer compound" means a compound having a structure in which a plurality of plural structural units are repeated in a molecule, and includes a so-called dimer. On the other hand, "low molecular compound" means a compound having no identical structural unit in a molecule. <Polymer compound (A) > 323899 9 201246553 The organic thin film transistor insulating layer material of the present invention contains a polymer compound having a plurality of functional groups which absorb electromagnetic wave energy or electron beam energy to cause dimerization reaction There are a plurality of first functional groups that generate a second functional group that reacts with active hydrogen when electromagnetic waves or heat are applied. In the second book, the (four) magnetic wave energy or electron beam energy is used to generate the dimerization reaction. The s energy group is called the "photodimerization reaction group". Further, in the present specification, "tongue hydrogen" means a hydrogen atom bonded to an oxygen atom, a sulfur atom or a nitrogen atom. ^ In the form - the photodimerization reaction system is a functional group that can react synergistically when absorbing light energy or electron beam: The functional groups which can be synergistically reacted with each other to be dimerized by the formation of a crosslinked structure inside the insulating layer. ^If the electromagnetic wave absorbed by the photodimerization reaction group is low energy, when the organic germanium film dielectric insulating layer material is formed by photopolymerization, the photodimerization reaction group also reacts. Therefore, it is preferably high energy light. . Preferably, the electromagnetic wave absorbed by the photodimerization reaction group is ultraviolet light having a wavelength of 4 Å or less, preferably 150 to 390 nm, more preferably 28 Å to 38 Å. Here, dimerization means that the molecules of two organic compounds form a chemical bond. The molecules of the bond may be the same or different from each other. The chemical structures of the functional groups related to dimerization in the two molecules of dimerization may be the same or different from each other. However, the functional group is preferably a structure which can produce a photodimerization reaction and a combination thereof without using a reaction aid such as a catalyst or an initiator. This is because if the residue of the reaction aid is contacted, the surrounding organic material may be deteriorated. The first functional group contained in the polymer compound does not react with active hydrogen. However, when the first functional group is subjected to electromagnetic waves or heat, a second functional group is formed, which reacts with active hydrogen. That is, the above-mentioned third functional group is deprotected by magnetic waves or heat by electricity 323899 10 201246553, and a second functional group which reacts with active hydrogen is generated. The second functional group reacts with and bonds with the active hydrogen-containing group of the active hydrazine compound (E), whereby a crosslinked structure can be formed inside the insulating layer. In the present specification, "active hydrogen compound" means a compound having more than one active application. In the step of forming the gate insulating layer, the second functional group is protected (blocked) until electromagnetic waves or heat are applied, and is present as a first functional group in the organic thin film transistor insulating layer material. This result enhances the storage stability of the organic thin film transistor insulating layer material. For example, a polymer compound containing a repeating unit having a photodimerization reactive group and a repeating unit having the above-mentioned first g of the group corresponds to the above-mentioned high molecular compound. The repeating unit having a photodimerization reaction group is preferably a repeating unit represented by the above formula (1). The polymer compound contained in the organic thin film transistor insulating layer material of the present invention preferably contains a polymer compound having a repeating unit represented by the formula (1) and a repeating unit having a first functional group. Such a polymer compound is referred to as a polymer compound (A). In the formula (1), R2 represents a hydrogen atom or a methyl group. In one form, r2 is a thiol group. In the formula (1), 'R3 and I each independently represent a divalent organic group having 1 to 2 carbon atoms. The hydrogen atom of the valence organic base towel may be substituted with a domain atom. The valence organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be saturated or unsaturated. The anti-number 1 to one-valent organic group may, for example, be a carbon number of 1 to 20 323899

2012 S 201246553 A linear hydrocarbon group, a branched hydrocarbon group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 2 carbon atoms, and an aromatic hydrocarbon group having 6 to 2 G, preferably having a carbon number i to 6 a linear hydrocarbon group, a branched hydrocarbon group having 3 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. A linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 2 carbon atoms and a cyclic hydrocarbon group having 3 to 20 carbon atoms, and a hydrogen atom contained in the group may be substituted with a fluorine atom. The aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted by an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. Specific examples of the one-valent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tert-butyl group, and cyclopropyl group. Cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthracenyl, fluorenyl (t〇lyl), Xylyl, dimethylphenyl, trimethyl, ethyl, diethylphenyl, triethylphenyl, propylphenyl, butylphenyl, methylnaphthyl , dimethylnaphthyl, trimethylnaphthyl, vinylnaphthyl, ethenylnaphthyl, decyl fluorenyl, ethyl fluorenyl, phenyl, bromo. The one-valent organic group having 1 to 20 carbon atoms is preferably an alkyl group. The carbon atom in I may be bonded to a carbon atom in R4 to form a 5-membered ring or a 6-membered ring. The 5-membered ring may be a cyclohexene ring. In one embodiment, R3 and R4 are the same or different ones selected from the group consisting of methyl and ethyl groups. In the formula (1), Rbb represents a linking main chain and a side chain, and may have a fluorocarbon 323899 12 201246553

The link between the children. The linking portion may be a divalent group having a structure which does not exhibit reactivity under the environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention. Specific examples of the linking portion include a bond composed of a divalent organic group having 1 to 20 carbon atoms, a bond (·〇-), a ketone bond (-CO-), and an ester bond (-coo-, - OCO·), amidoxime linkage (-NHCO-, -CONH-), a urethane bond (-NHCOO-, -OCONH-), and a bond combination of these bonds. c represents an integer of 〇 or 1. In one form c is 1. 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 group or an aromatic hydrocarbon group. For example, a divalent linear aliphatic hydrocarbon group having a carbon number of i to 20, a divalent branched aliphatic hydrocarbon group having 3 to 2 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituted alkyl group or the like The slave number is 6 to 20 one-valent aromatic hydrocarbon group. 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, a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkyl group, etc. A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted. Specific examples of the divalent aliphatic hydrocarbon group and the divalent cyclic hydrocarbon group include methylene, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and Butyl, dimethyl-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Specific examples of the divalent aromatic hydrocarbon group having an inverse number of 6 to 20 in the stone include t, an onion group, a dif-phenylene group, a trimethylphenyl group, a di-I-, a di-ethyl-phenyl group, and a tri-ethyl group. Base phenyl, propyl extended base, butyl extended phenyl, phenyl-naphthyl, hexyl, phenyl aryl, 323899 13 201246553 methyl fluorenyl, methyl anthranyl, ethylene anthranyl, vinyl Naphthyl, ethyl anthracenyl. Preferred materials for the photodimerization reaction group are a group of a gas atom of a maleimine group = 1 ΠΠ = 3 and a group of a gas atom of 4 positions which are each substituted by a group or a group, and a group represented by 4 (5). The towel of the formula (5), r, is preferably a propane-1,3-diyl group, a Dingyuan_, a 4-diyl group.

(5) In the formula (5), R' represents the second base. When the photodimerization reaction group is a hydrogen atom at the 3-position of the maleimine group and a hydrogen atom at the 4-position each substituted by an alkyl group or an aryl group, or a group represented by the formula (5), when ultraviolet rays or electrons are irradiated The beam undergoes a 2 + 2 cyclization reaction and crosslinks the organic thin film transistor insulating layer material. Further, preferred examples of the above first functional group include an isocyanate group blocked by a blocking agent and an isothiocyano group blocked by a blocking agent. The above-mentioned isocyanato group blocked by a blocking agent or the above-mentioned isothiocyanyl group blocked by a blocking agent can be obtained by having only one isocyanic group or isothiocyanato group in one molecule. A blocking agent for the active hydrogen of the reaction is produced by reacting with an isocyanate group or an isothiocyanate group. In the meantime, the blocker is preferably dissociated at a temperature below 170 ° C even after reacting with an isocyanato group or an isothiocyanate group 323899 14 8 201246553. Examples of the blocking agent include an alcohol compound, a phenol compound, an active methylene compound, a thiol compound, a guanamine compound, and an acid imine compound. A rice squat compound, a urinary compound, an oxime compound, an amine compound, an imine compound, a bisulfite salt, a ° ratio compound, and a 0-ratio beta compound. These blocking agents may be used singly or in combination of two or more. Preferred blocking agents include an anthraquinone compound and a pyrazole compound. Specific blockers are exemplified below. Examples of the alcohol-based compound include decyl alcohol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl quercetin, decyl carbitol, and benzyl alcohol. , cyclohexanol. Examples of the phenolic compound include phenol, cresol, ethylphenol, butanol, indophenol, dinonylphenol, styrenated phenol, and hydroxybenzyl ester. Examples of the active fluorenylene-based compound include didecyl malonate, diethyl malonate, ethyl acetonitrile acetate, ethyl acetate acetate, and acetamidine. Examples of the thiol compound include butyl mercaptan and dodecyl mercaptan. Examples of the guanamine-based compound include acetaminophen, acetamide, ε-caprolactam, valeroguanamine, and butyrolactam. Examples of the quinone imine compound include a succinimide and a maleimide. Examples of the imidazole-based compound include imidazole and 2-indolyl saliva. Examples of the urea-based compound include urea, sulfur urea, and ethyl urea. Examples of the amine compound include diphenylamine, aniline, and carbazole. Examples of the imine compound include an ethylenimine and a polyethylenimine. An example of the bisulfite salt is sodium bisulfite. Examples of the pyridinium compound include a 2-pyro group π ratio bite and a 2-passage group. Examples of the 323899 15 201246553-based compound are exemplified by 曱(iv), ethyl domain, propyl ketone, butyl hydrazine, and cyclohexanone oxime. Examples of the pyrazole-based compound include 3 5 -pyrazole and 3,5-diethylpyrazole. The thiol group or the isothiocyanyl group which is blocked by the blocking agent used in the present invention is preferably a group represented by the above formula (3) or a group represented by the above formula (4). In the formulae (3) and (4), Xa represents an oxygen atom or a sulfur atom, and 乂匕 represents that the oxygen atom or the sulfur atom U r9 is the same or different, and represents a hydrogen atom or a one-valent organic group having 1 to 20 carbon atoms. The definition, specific examples, and the like of the monovalent organic group are the same as those of the above-mentioned monovalent organic group, specific examples, and the like. In one embodiment, R5 to R9 are a hydrogen atom. Examples of the isocyanato group blocked by the blocking agent include 〇-(methylideneamino)carboxyamino, 〇-(ethylideneamino)carboxyamine. Base, 〇_〇_methylethylidene), sulfhydryl, 0-[1-methylpropyleneamino]alkyl, (Ν_3,5-dimethylpyrazolylcarbonyl) Amino, (indol-3-ethyl-5-methylpyrazolylcarbonyl)amino, (Ν-3,5-diethylpyrazolylcarbonyl)amine, (ν-3-propyl-5) -Methyl 0 is more than anthranyl)amino, (indol-3-ethyl-5-propylπ-indenyl)amino group. Examples of the isothiocyano group blocked by the blocking agent include 〇-(methyleneamino)thiocarboxyamino group, 0-(1-ethylideneamino)thiocarboxyamino group, hydrazine- (1-methylethylideneamino)thiocarboxyamino, 0-fluorenyl-mercaptopropylamino]thiocarboxyamino, (N-3,5-dimethyln-pyrazolylsulfide Alkylcarbonyl)amino, (indol-3-ethyl-5-methyl 0 to 0-ylthio-reactive) amine, (Ν-3,5-diethylpyrazolylthiocarbonyl)amino , (Ν-3-propyl-5-methylpyrazolylthio 323899 16 8 201246553 propyl propyl thiol) amino group. The rammed earth is preferably isocyanate blocked by a blocking agent. For example, a method of copolymerizing a polymerizable human first-functional polymerizable monomer which is a raw material of a repeating unit represented by the above formula (1) by using a photopolymerization initiator or a thermal polymerization may be used. (A). The polymerization of the polymerizable monomer is usually used in the field. The polymerization method of the polymerizable monomer is, for example, a method in which a polymerizable body and a polymerization initiator are dissolved in a suitable solvent, and oxygen contained in the resulting solution is replaced with an inert gas, followed by heating or irradiation for a certain period of time. An example of a polymerizable monomer which is a raw material of a repeating unit represented by the above formula (1) is N-(3,-methylpropenyloxypropyl)·3,4-dimethyl malay醯iamine, Ν-(3,-mercaptopropenyloxypropyl)_;!_ % 己- ( 3methacryloyloxypropyl -1 -cyclohexene· 1, 2-dicarboximide). Examples of the polymerizable monomer having a first functional group include an isocyanato group blocked by a blocking agent or an isothiocyanyl group blocked by a blocking agent, and a saturated-bonded monomer having an isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturatedly bonded monomer, which may have an isocyanate The acid group or the isothiocyanato group and the unsaturatedly bonded compound are produced by reacting with a blocking agent. The unsaturated bond is preferably a double bond. Examples of the compound having a double bond and an isocyanate group include: 2-propenylmethoxyethyl isocyanate, 2-mercaptopropenyloxyethyl iso 323899 17 201246553 Cyanate, 2-(2'-methylpropenyloxyethyl)oxyethyl Cyanic acid vinegar. Examples of the compound having a double bond and an isothiocyana group include 2-propenylmethoxyethyl isothiocyanate and 2-methylpropenyloxyethyl isosulfide. Cyanate ester, 2-(2'-fluorenyl fluorenyl methoxyethyl) oxyethyl isothiocyanate. The blocking agent contained in the polymerizable monomer can be suitably used as the above-mentioned blocking agent. In the monomer having an isocyanato group blocked by a blocking agent or an isothiocyanate group blocked by a blocking agent and an unsaturated bond, an organic solvent, a catalyst, or the like may be added as necessary. Examples of the monomer having an isocyanate group and a double bond blocked by a blocking agent include 2-[0-[1'-mercaptopropylamino]carboxyamino]ethyl-anthracene Acrylate, 2-[Ν-[Γ,3'-dimethylpyrazolyl]carbonylamino]ethyl-mercapto acrylate. The above-mentioned isothiocyano group blocked by a blocking agent Examples of the monomer of the double bond include 2-[0-[1'-methylpropyleneamino]thiomethylamino]ethyl-methacrylate, 2-[N-[l' ,3'-dimercaptopyrazolyl]thiocarbonylamino]ethyl- Examples of the acryl acrylate and the photopolymerization initiator include acetamidine, 2,2-dimethoxyoxy-2-phenylethyl benzene, 2,2-diethoxyethyl benzene, and 4 -Isopropyl-2-hydroxy-2-mercaptopropenylbenzene, 2-hydroxy-2-methylpropenylbenzene, 4,4'-bis(diethylamino)diphenyl ketone, diphenyl Ketone, methyl (o-benzylidene) benzylate, 1-n-yl-1,2-propanedifluorene-2-(0-ethoxylated), 1-n-yl-1,2-propane Keto-2-(o-benzylidene) hydrazine, benzoin, benzoin decyl ether, 323899 18 8 201246553 • Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, rest "cetyl ether" a carbonyl group compound such as diphenylethylenedione (bend), diphenylethylenedione dimethyl ketal, diphenylethylenedione diethyl ketal, diacetyl, etc. Chloroquinone, chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl xanthone and other brewing derivatives or xanthene derivatives 'diphenyl disulfide, dithio A sulfur compound such as an amine phthalate. When the light 3b is used as the energy for starting the bonding, the wavelength of the light irradiated to the polymerizable monomer is 360 nm or more', preferably from wo to 45 Å. The above-mentioned thermal polymerization initiator may be any compound which can be used as a starter for radical polymerization, and examples thereof include 2,2,-azobisisobutyronitrile and 2,2,_azobisisoamyl. Nitrile, 2,2'-azobis(2,4-dimethyl ketone), 4,4, azobis(4-cyanovaleric acid), 1,1M horse nitrogen double (cyclohexene burned) , 2,2,-azobis(2-mercaptopropane), 2,2,-azobis(2_mercaptopropionyl) 2 hydrochloride, and other azo compounds, peroxybutyrate, Peroxidic oxime isobutyl sulfoxide, cyclohexanone peroxide, acetoxyacetone acetone, etc., isobutyl peroxide, ruthenium peroxide, peroxy 2,4·dichloro(tetra), peroxidation O-Methyl fluorenyl group, oxidized lauryl sulfhydryl group, peroxidic p-chlorobenzyl group, etc., 2-hydroperoxide 2,4,4-trimethylpentyl (2' 4,4-trimethylpentyl-2-hydr〇peroxide), diisopropylbenzene hydroperoxide, cumene hydroperoxide, hydrogen peroxide, third base, etc. Hydrogen species: dicumyl peroxide , tributyl cumyl peroxide, peroxy = tert-butyl, tris (t-butyl peroxide) triterpene Peroxydicarbonate, 1,1-di-peroxide, tert-butylcyclohexane, 2,2-di (peroxidation 323899 201246553 tributyl) butane, etc. Tert-butyl valerate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, di-tert-butyl peroxydibenzoate, ruthenium peroxide Dibutyl tert-butylate, tert-butyl peroxy-3,5,5-tridecylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzylate, tridecyl peroxide An alkyl perester such as dibutyl succinate, diisopropyl peroxydicarbonate, dibutyl butyl dicarbonate, and tert-butyl peroxy isopropyl carbonate. Oxycarbonic acid. The polymer compound (A) used in the present invention can be added by adding a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (1) and a polymerizable monomer having a first functional group at the time of polymerization. Manufactured from a polymerizable monomer. Examples of the additional polymerizable monomer include acrylic acid acrylate and its derivatives, mercapto acrylate and its derivatives, styrene and its derivatives, vinyl acetate and its derivatives, mercapto acrylonitrile and its derivatives. , 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, maleic acid Dialkyl vinegar and its derivatives, dialkyl esters of itaconic acid and its derivatives, N-vinylamine derivatives of organic carboxylic acids, terminally unsaturated hydrocarbons and their derivatives, etc. A saturated hydrocarbon group of a germanium derivative or the like. The type of the polymerizable monomer to be additionally used is appropriately selected in response to the characteristics required for the insulating layer. From the viewpoint of excellent durability to a solvent and a small hysteresis of an organic thin film transistor, such as styrene or styrene derivative 323899 20 ^ 8 201246553 organism, in the presence of these compounds, the molecular density is selected to be high and formed. Hard. Monomer of the membrane. Further, from the viewpoints of the adhesion of the gate electrode or the surface of the substrate, etc., and the adhesion of the junction, such as mercapto acrylate and its derivatives, turtle acrylate and its derivatives, the polymer compound is selectively added ( A) Plasticity monomer. As the acrylates and derivatives thereof, monofunctional acrylates can be used, although polyfunctional acrylates can also be used, and such monofunctional acrylates or polyfunctional acrylates include, for example, acrylonitrile. Acid ester, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, dibutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate , decyl acrylate, isodecyl acrylate, cyclohexyl acrylate, isopropyl acrylate, benzyl acrylate, acrylic acid 2-trans-glycol, acrylic acid _2 _ _ _ _ _ _ _ _ 3 - propyl acetoacetate, 2-hydroxybutyl acrylate, 2 - hydroxyphenyl ethyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, Diethylene glycol diacrylate, triethylene glycol dipropionate, tri-propyl mercapto-acrylic acid vinegar, tri-propyl mercapto triacetate, neopentyl alcohol pentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(acrylic acid) Fluorobutyl)ethyl ester, 3-perfluorobutyl 2-propyl permethacrylate, 2-(perfluorohexyl)ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-(acrylic acid) Perfluorooctyl)ethyl ester, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluoro-3-mercaptobutyl)ethyl acrylate , 3-(Perfluoro-3-mercaptobutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, 323899 21 201246553 Acrylic acid 2-(perfluoro- 3-mercaptobutyl)-2-carbyl propyl, 3-(perfluoro-5-fluorenylhexyl)-2-propanyl acrylate, 2-(perfluoro-7-fluorenyl) acrylate Ethyl)ethyl ester, 3-(perfluoro-7-fluorenyloctyl)-2-hydroxypropyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, ih,1H,5H-octafluoropentyl acrylate , 1H,1H,7H-dodecylheptyl acrylate, ιη,1Η,9Η·hexadecafluorodecyl acrylate, 1Η-1-(trifluoromethyl)trifluoroethyl acrylate, 1 Η, 1Η, 3Η_6 Fluorine, hydrazine, hydrazine-dimethyl methacrylate, ν, Ν-diethyl acrylamide, N-acryl〇yl morpholine. Monofunctional methacrylates can be used for mercapto acrylates and their derivatives, although polyfunctional methacrylates can be used, such as monofunctional methacrylates or polyfunctional methacrylates. Examples of the acrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methyl group. Dibutyl acrylate, hexyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate , phenyl methacrylate, benzyl methacrylate, _2 hydroxyethyl methacrylate, methacrylic acid -2- propyl acrylate, methacrylic acid _3_ propyl group, methyl propylene Acid-2-hydroxybutyl ester, 2-hydroxyphenylethyl methacrylate, ethylene glycol dimethacrylate, propanol dimethacrylate, i, 'butanediol dimercaptopropene oxime , ethyl alcohol dimethacrylate, triethylene glycol dimethacrylate, three Methyl propyl methacrylate, trisyl propyl trimethyl acrylate, neopentyl alcohol pentamethacrylate, methacrylic acid 2,2,2-difluoroethane 2,2,3,3,3_pentafluoropropyl methacrylate, methyl propylene 323899 8 22 201246553 2-(perfluorobutyl)ethyl enoate, 3_perfluorobutyl _2 methacrylate Hydroxy, propyl ester, 2-(perfluorohexyl)ethyl methacrylate, 3-methacrylic acid, perfluorohexyl-2-hydroxypropyl ester, 2-(perfluorooctyl)ethyl methacrylate, * fluorenyl 3-Perfluorooctyl-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-mercaptobutyl)ethyl decyl acrylate, fluorenyl 3-(perfluoro-3-mercaptobutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-fluorenylhexyl)ethyl methacrylate, 2-propanyl-methyl acrylate 3-mercaptobutyl)-2-hydroxypropyl ester, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-fluorenyl octyl acrylate) Ethyl ester, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, methacrylate 1Η,5Η-octafluoropentyl ester, 1H,1H,7H-dodecylheptyl methacrylate, 1H, 1H, 9H-hexadecafluorodecyl methacrylate, 1H-1-(trifluoromethyl) methacrylate Trifluoroethyl ester, mercaptoacrylic acid 1H, 1H, 3H-hexafluorobutyl ester, N,N-dimethylmethacrylamide, N,N-diethylmercaptopropenylamine, N-oxime Examples of styrene and its derivatives include styrene, 2,4-dimethyl-α-methylstyrene, o-nonylstyrene, m-methylstyrene, and para Styrene, 2,4-dimethylstyrene, 2,5-dimercaptostyrene, 2,6-dimercaptostyrene, 3,4-dimethylstyrene, 3,5-dimethyl Styrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentadecylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylbenzene Ethylene, o-chlorostyrene, m-gas styrene, p-styrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-nonyloxystyrene, m-methoxystyrene, p-methoxyl 323899 23 201246553 Styrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxyphenyl , 2-ethylene biphenyl, 3-ethylene biphenyl, 4-ethylene biphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-ethylene p-triphenyl, 1-vinyl anthracene, methyl styrene, o-isopropenyl Toluene, m-isopropenylbenzene, p-isopropenyltoluene, 2,4-dimethyl-α-mercaptostyrene, 2,3-dimercapto-fluorene-methylstyrene, 3,5 - dimethyl-α-mercaptostyrene, p-isopropyl-fluorenyl ethylene, ethyl styrene, α-styrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4 - Aminostyrene. Examples of the organic phthalic acid ethyl ester and derivatives thereof include ethyl acetate, ethyl propionate, acetonitrile, ethyl benzylate, and diethylene adipate. Examples of the organic retinoic acid propyl ester and derivatives thereof include isopropyl propyl acetate, allyl benzylate, diallyl adipate, diisopropyl propyl phthalate, and isophthalic acid. Allyl ester, diallyl phthalate. Examples of the tert-butyl ester of fumaric acid and derivatives thereof include dimethyl dibutyl succinate, diethyl fumarate, diisopropyl glutaric acid, and anti-butadiene Dibutyl succinate, diisobutyl succinate, di-n-butyl succinate, di-2-ethylhexyl fumarate, succinic acid Purpose. Examples of the dialkyl ester of maleic acid and derivatives thereof include dinonyl maleate, diethyl maleate, diisopropyl maleate, maleic acid, second butane vinegar, and Malay. Diisobutyl S, di-n-butyl maleate, di-ethylhexyl maleate, dibenzyl maleate. Examples of the dialkyl ester of itaconic acid and derivatives thereof include: itaconic acid 24 323899 8 r 201246553 - diterpene ester, diethyl itaconate, diisopropyl itaconate, and itaconic acid Dibutyl ester, diisobutyl amiconate, di-n-butyl itaconate, di-2-ethylhexyl orconate, dibenzyl itaconate. * An example of the N-vinylamine derivative of the organic carboxylic acid is N-methyl-N-ethyleneacetamide. Examples of the terminal unsaturated hydrocarbon and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, ethylene cyclohexane, vinyl chloride, and allyl alcohol. Examples of the organic anthracene derivative containing an unsaturated hydrocarbon group include allyltrimethylhydrazine, allyltriethylsulfonium, allyltributylphosphonium, trimethylstilbene oxime, and triethylethenephosphonium. . Among these, acryl based S, mercapto acrylate styrene, styrene, acrylonitrile, mercapto acrylonitrile, allyl tridecyl fluorene are preferred. The molar ratio of the polymerizable monomer which is a raw material of the repeating unit represented by the formula (1) is 5 mol% or more and 50 mol% or less, preferably 10 mol%, based on all the monomers related to the polymerization. The above 45 mol% or less, more preferably 20 mol% or more and 40 mol% or less. By adjusting the addition molar ratio of the above monomers to be in this range, a crosslinked structure is sufficiently formed inside the insulating layer to keep the polar group content low, and to suppress polarization of the insulating layer. The molar ratio of the addition of the polymerizable monomer having the first functional group is 5 mol% or more and 50 mol% or less, preferably 10 mol% or more and 40 mol% or less, based on all the monomers related to the polymerization. More preferably, it is 15 mol% or more and 30 mol% or less. By adjusting the addition molar ratio of the above monomers to be in this range, the crosslinked structure is sufficiently formed inside the insulating layer to keep the polar group content low and to suppress the polarization of the insulating layer. 323899 25 201246553 The oxime molecular compound (A) preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 5 Å in terms of polystyrene, and is linear, branched or ring-shaped. Can be. The polymer compound (A) is exemplified by poly(styrene_copolymer_[N_(3-mercaptopropenylmethoxypropyl-3',4'-didecylmaleimine)]-copolymer -[2-[0-(1'-methylpropyleneamino)carboxyamino]ethyl-mercapto acrylate]), poly(styrene-co-[N·(3-mercaptopropene oxime) Hydroxypropyl-3',4'-diindenyl malay turtle imine)]-copolymerization_[2_[ ι,_( 3,5,1-dimethyl B-pyrazolyl)carbonylamino] Ethyl-methacrylate]), poly(styrene-co-[N-(3-methylpropenyloxypropyl_3',4,-didecylmaleimide)]- Copolymer-acrylic guess-co-[2-[〇-(1'-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(styrene-copolymer-[N- (3-mercaptopropenyloxypropyl_3',4,-dimethylmaleimide)]-co-acrylonitrile-copolymer-[2-[ Γ- (3,,5,- Dimercaptopyrazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(stupyl-co-co-[N-(3-mercaptopropenyloxypropyl-3', 4'_ Diterpene-based maleimide)]-co-acrylonitrile-co- -[2-[〇-(1,_Methylenepropylamino)carboxyamino]ethyl_ decyl acrylate]-co-allyl trimethyl hydrazine), poly(styrene-copolymerization [N-(3-Mercaptopropenyloxypropyl-1'-cyclohexene-1', 2'-dimethylimine])-co-acrylonitrile copolymer-[2-[ 1,-- (3',5,-Dimethylcarbazolyl)carbonylamino]ethyl decyl acrylate]-co-allyl trimethyl hydrazine), poly([N-(3-mercaptopropene fluorene) Hydroxypropyl-1'-cyclohexene-indole, 2'-dimethylimine imine)]-co-[2-[indol-(1,-methylpropylideneamino)carboxylamino] Ethyl-methyl acrylate [), poly([Ν-(3-mercaptopropyl propyl propyl propyl 323899 26 8 201246553 -1 cyclohexene-1 ', 2'-dimethyl hydrazine Amine)]-copolymer-[2-[ 1 '- ( 3,5,-dimethyl 1»- sylylene) benzylamino]methyl-methyl acrylate]), poly(phenyl Women-copolymer-[N-(3-methylpropanyloxypropyl_ι'_cyclohexene q,,],-dimethylanilinium)]-co-[2-[0- (1,-decyl propyleneamino) tetamine amino]ethyl-methacrylic acid vinegar]), poly(benzene Ethylene·copolymerization_[N_(3曱-propylglycolyloxypropyl-1'-cyclohexyl dimethoxyimino)]-co-[2-[1'-(3',5'- Dimercaptocarbazolyl)carbonylamino]ethyl-methyl propyl ester]) and the like. <Polymer Compound (B)> The polymer compound contained in the organic thin film transistor insulating layer material of the present invention preferably has a plurality of photodimerization reactive groups, has a fluorine atom, and has a plurality of The macromolecular compound of the above fluorene functional group. The polymer compound particularly has a repeating unit represented by the formula (丨), a repeating unit represented by the formula (2), and a polymer compound having a repeating unit of the i-th functional group. Such a polymer compound is called a high component (B). The insulating layer formed of the material is made to have a low polarity by suppressing T and gas in the organic thin film transistor insulating layer material, and the polarization of the insulating layer is suppressed. Further, if a crosslinked structure is formed inside the insulating layer, the molecular structure is suppressed and the polarization of the insulating layer is suppressed. If the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the hysteresis of the organic thin film transistor is lowered to improve the operation accuracy. The fluorine atom is preferably a hydrogen atom which does not replace the main chain of the polymer compound, and the hydrazine replaces a hydrogen atom of a side chain or a pendant gr〇up. If the fluorocarbon 323899 201246553 substituting the cis or side binder reduces the affinity for other organic materials such as the organic (tetra) body, the organic material contacts the exposed surface of the insulating layer in the layer containing the organic material, so that the layer The formation is easy. For example, the polymer compound (B) is a polymer compound including a repeating unit having a fluorine atom-containing group, a repeating unit having a photodiodizing group, and a repeating unit having the above i-th functional group. A preferred example of the fluorine atom-containing group is a phenyl group in which a hydrogen atom is substituted with a fluorine-substituted aryltrihydrogen atom via a fluorine group, particularly a phenyl group in which a hydrogen atom is substituted by a gas, and a phenyl group in which an argon atom is substituted by fluorine. Preferred examples of the photodimerization reaction group include a repeating unit having a fluorine atom-containing group in the above-mentioned phase, and preferably a soil. Represents a repeating unit. In one form of the formula (2), in the formula (2), 'R丨 represents a nitrogen atom or a fluorenyl group represents a hydrogen atom. In the formula (2), Rf represents a fluorine atom or a one-valent organic group having a good atom. In one embodiment, Rf is a fluorine atom. And the numbers 1 to b represent integers from 1 to 5. In one form, b is $

When Rf is an organic lanthanum having 1 to 20 carbon atoms of a fluorine atom, the number of carbon atoms of the atom is 1 to 20, and the organic group may be exemplified by trifluoromethyl having fluorotrifluoroethyl, 2, 2, 3, 3, 3 Pentafluoropropyl, 2-(perfluorobutyryl, 2,2,2, fluorophenyl, trifluoromethylphenyl, etc.. In the ethyl group, the formula (2), 'R represents a hydrogen atom or a carbon number of 1 To the base. 20 to 1 organic R is a carbon number of 1 to 20 one-valent organic group, the - 323899 only the machine base does not have

28 N 201246553 There are fluorine atoms. R represents a one-valent organic group having 1 to 20 carbon atoms, and examples of the organic compound having a carbon number of 1 to 20 represented by R3 include a group having no fluorine atom. In the formula (2), Raa represents a main chain and a side chain, and may have a linking moiety of a fluorine atom. The linking portion may be a divalent group having a structure which does not exhibit reactivity under the environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention. In the specific example of the linking moiety, the bond composed of the divalent organic group having 1 to 20 carbon atoms may be exemplified by an ether bond (-〇-), a ketone bond (-CO-), and an ester bond (-COO-). , -OCO-), amidino group linkage (-NHCO-, -CONH-), an amine phthalate linkage (-NHCOO-, -OCONH-), and a bond of the bonding. u represents an integer of 0 or 1. In one form, a is one. The divalent organic group having 1 to 20 carbon atoms is the same as the specific example of the divalent organic group having 1 to 20 carbon atoms represented by Rbb. For example, polymerization of a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (1) and a raw material which is a repeating unit represented by the above formula (2) can be obtained by using a photopolymerization initiator or a thermal polymerization initiator. The polymer compound (B) is produced by a method of copolymerizing a monomer and a polymerizable monomer having a first functional group. Examples of the polymerizable monomer which is a raw material of the repeating unit represented by the above formula (2) include 2-trifluorodecylstyrene, 3-trifluorodecylstyrene, 4-trifluorodecylstyrene, and 2 , 3,4,5,6-pentafluorostyrene, 4-fluorostyrene. The polymer compound (B) which can be used in the present invention can be added by polymerizing a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (1), a 323899 29 201246553 monomer, and a monomer. In the above-mentioned formula (1), the material of the repeating unit has a polymerizable single-phase polymerization of the first main filament, and the amount of the polymer compound (B) is adjusted to be adjusted to the amount represented by the above formula (7). The amount of monomer used. The amount of the fluorine atom introduced into the molecular compound (8) in the raw material of the late morning element relative to the polymer compound (B) is preferably from 7% to 7% by mass, and more preferably from U) to The quality /,; 6, more preferably 5 to 1% by mass, there will be insufficient effect of reducing the amount of the unresolved phenomenon of the gas atom of the ray, and if it exceeds the affinity of the lag conductor material of the 1_membrane transistor The property is degraded, and the activity + is reduced by the use of the polymer compound (B). From the viewpoint of the absolute value of the threshold voltage: when the number of repeating units of the film transistor is (10), the amount of the repeating unit represented by the formula (2) is preferably: to two (8) having a smaller amount than the molecular compound (8) The weight average molecular weight in terms of polystyrene is 3,000 to 100,000 (ppm), more preferably 5,000 to 500,000, and it may be linear, branched or ring-shaped. The fluorene molecular compound (B) is exemplified by poly(styrene-co-[N_^3-mercaptopropenyloxypropyl_3',4,-didecylmaleimide)]_5 Istyrene-copolymerization, [2·[〇_(1'-methylpropylideneamino)carboxylidene]ethyl-methacrylic acid vinegar]), poly(styrene-copolymerization (3· Methyl bis-decyloxypropyl·3',4'.dimethyl-maleimine)]_Copolymer·323899 201246553 • Pentafluorostyrene-copolymer-[2-[ 1,-(3, ,5,-didecyl 0-oxazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[N_(3-methacrylic)-decyloxypropyl-3 ,,4,-dimercaptomaleimide)]_co-pentafluorobenzene

I • olefin copolymer-acrylonitrile-copolymer-[2-[ Ο-( Γ-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(styrene-copolymer-[N - (3-mercapto-propyl-glycolyloxypropyl-3',4'-dimethylmaleimide)]-co-pentafluorostyrene-co-acrylonitrile-copolymer-[2-[ Γ-(3',5'-diindolyl "bazolyl" carbonylamino]ethyl-mercapto acrylate]), poly(styrene·co-[Ν-(3-mercaptopropenyloxy) Propyl-3',4'-dimercaptomaleimide)]-co-pentafluorostyrene-co-acrylonitrile-copolymerization_[2-[ Ο-( Γ-mercapto propyleneamine Carboxyamino]ethyl··decyl acrylate]-co-allyl trimethyl fluorene], poly(styrene-co-[--(3-mercaptopropenyloxypropyl-) Γ-cyclohexene-l',2'-diimineimine)]-co-pentafluorostyrene-co-acrylonitrile-copolymer-[2-[1'-(3',5'-dioxin Pyrazolyl)carbonylamino]ethyl-mercapto acrylate]-co-allyl tridecyl fluorene), poly([Ν-(3_methacryloyloxypropyl_1'_) Cyclohexene diimine imine)]-co-pentafluoro Styrene-copolymer-[2-[〇-(1,methylpropyleneamino)carboxyamino]ethyl-mercapto acrylate]), poly([Ν-(3-methylpropenyloxy) Propyl-1'-cyclohexene-1,2'-dimethylimine]]-co-pentafluorostyrene-copolymer-[2-[ Γ-(3',5'-didecyl) Pyrazolyl)carbonylamino]ethyl-methacrylate]), poly(styrene-co-(4·trifluoromethylstyrene)-co-[Ν-(3-methylpropenyloxy) Propyl-1'-cyclohexene-1', 2'-diimineimine)]-co-[2-[0-(Γ-methylpropylideneamino)carboxyamino]ethyl -mercapto acrylate]), poly(styrene-co-(4-trifluoromethylstyrene)-copolymer-[Ν- 323899 31 201246553 (3-mercaptopropenyloxypropyl-1'- Cyclohexene-fluorene, 2'-diimineimine)]-co-[2-[1'-(3',5'-didecyloxazolyl)carbonylamino]ethyl-mercaptoacrylic acid Ester]) and so on. <Polymer Compound (C) > Other preferred embodiments of the polymer compound contained in the organic thin film transistor insulating layer material of the present invention have a plurality of photodimerization reactive groups and a plurality of the above first functional groups A polymer compound having two or more active hydrogen groups. Such a polymer compound is called a polymer compound (C). The active hydrogen may be bonded directly or via a specific group bond to the main chain constituting the polymer compound. Further, the active hydrogen may be contained in each structural unit constituting the polymer compound, or may be contained only in a part of the structural unit. Further, the active hydrogen may be bonded only to the end of the polymer compound. Specific examples of the polymer compound (C) include a repeating unit represented by the formula (1), a repeating unit containing a first functional group, and a polymer compound having two or more structural units containing one active hydrogen; A polymer compound represented by the formula (1), a repeating unit containing a first functional group, and a structural unit containing two or more active hydrogens. For example, a monomer having an unsaturated bond such as a group containing an active hydrogen and a double bond, and a polymerizable monomer which is a raw material of the repeating unit represented by the above formula (1) and a polymerizable group containing the first functional group can be used. The monomer compound is copolymerized to produce a polymer compound (C). Further, a polymerizable monomer which is a raw material having an unsaturated bond such as a group containing an active hydrogen and a double bond, a raw material which is a raw material of the repeating unit represented by the above formula (1), and a polymerization containing the first functional group can be polymerized. It is produced by adding a polymerizable monomer other than a monomer. The polymerization 323899 32 8 201246553 can be used as a photopolymerization initiator or a thermal polymerization initiator. Further, the same as the above may be used as the polymerizable monomer, the photopolymerization initiator, and the thermal polymerization initiator. The monomer having an active hydrogen-containing group and an unsaturated bond may, for example, be an aminobenzene group, a phenyl group, a 7 gt; 丞 〇琊, a vinyl benzyl alcohol, an amino methacrylate Ester, ethylene glycol monovinyl ether, 4-hydroxybutyl acrylate. The polymer compound (C) has a weight average molecular weight of preferably from 3,000 to 1,000,000, more preferably from 5 to 5 Å, and may be linear, branched or cyclic. Either. The molar ratio of the polymerizable monomer having a first functional group and the monomer having an active hydrogen-containing group and an unsaturated bond used in the production of the sub-compound (C) is preferably 60/100 to 150/100, more preferably 70/100 to 120/100' and even more preferably 90/100 to 110/100. If the molar ratio is less than 60/100, the excess of active hydrogen causes the effect of reducing the hysteresis to be small. When it exceeds 150/100, the excess of the functional group reactive with the active hydrogen increases the absolute value of the threshold voltage. The polymer compound (C) is exemplified by poly(styrene-co-[Ν-(3-mercaptopropenyloxypropyl_3',4'-dimethylmaleimide)]- Copolymer·Aminostyrene-copolymer-[2-[0-(indolyl isopropylideneamino)carboxyamino]ethyl-methacrylate]), poly(styrene-copolymer-[Ν- (3-mercaptopropenyloxypropyl-3',4'-dimethylmaleimide)]-co-amino stupyl-co-polymer-[2-[ 1'-(3', 5,-Dimethyl π-oxazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-[Ν-(3-methylpropenyloxypropyl-3, , 4'-dimercaptopurineimine)]-co-aminostyrene-co-acrylonitrile-co-[2-[0-(Γ-methylpropylideneamino)carboxy 323899 33 201246553 Amino]ethyl-methacrylate]), poly(styrene·co-[N-(3-methylpropanyloxypropyl-3',4'-diindenyl mala Amine)]-co-aminostyrene-co-acrylonitrile-copolymer-[2-[ Ο-( Γ-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]-co-polymerization Allyl tridecyl锗), poly(styrene-co-[N-(3-mercaptopropenyloxypropyl-indole·cyclohexene-fluorene, 2'-dimethylimine)]-co-aminobenzene Ethylene·co-acrylonitrile-copolymer-[2-[ Γ·(3',5,-dimercaptopyrazolyl)carbonylamino]ethyl-methacrylate]-co-allyl tridecyl锗), poly([Ν-(3-mercaptopropenylmethoxypropyl-1'-cyclohexene-1', 2'-dimethylimine))-co-aminostyrene-copolymer -[2-[Ο-(1'-nonyl propyleneamino)carboxyamino]ethyl_methacrylate]), poly([Ν-(3-mercaptopropenyloxypropyl) -1'-cyclohexene-l',2'-diimineimine)]-co-aminostyrene-copolymer-[2-[ 1 '-(3',5'-dimercaptopyrazole Carboxyamino]ethyl-mercapto acrylate]), poly(aminostyrene-co-[Ν-(3-mercaptopropenyloxypropyl-l'-cyclohexene-fluorene, 2'-diimine imine)]-co-[2-[0-(1'-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(aminobenzene) Ethylene-copolymer-[Ν-(3-mercaptopropenyloxypropyl-1, cyclohexene_ 1,2,2-diimine)]-co-[2-[ 1,-(3,5,1-dimethylpyrazolyl)carbonylamino]ethyl-methacrylate]) Wait. <South Molecular Compound (D) > The polymer compound contained in the organic thin film transistor insulating layer material of the present invention preferably has a plurality of photodimerization reactive groups, fluorine atoms, and plural first A functional group and two or more polymer compounds containing a repeating unit of active hydrogen. Such a polymer compound is referred to as a high molecular compound (D) 323899 8 34 201246553. The active hydrogen may be bonded directly or via a specific base bond to the main chain constituting the polymer compound. Further, the active argon may be contained in each structural unit constituting the polymer compound, or may be contained only in a part of the structural unit. Further, the active hydrogen may be bonded only to the end of the polymer compound. Specific examples of the polymer compound (D) include a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), a repeating unit containing a first functional group, and two or more active hydrogen atoms. A polymer compound having a structural unit; a polymer compound having a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), a repeating unit containing a first functional group, and a structural unit containing two or more active hydrogens. For example, a polymerizable monomer which is a raw material of a repeating unit represented by the above formula (1), which has a monomer having an active hydrogen-containing group and an unsaturated bond, and the like, may be represented by the above formula (2). The polymerizable monomer of the raw material of the unit and the polymerizable monomer containing the first functional group are copolymerized to produce the polymer compound (D). In addition, a polymerizable monomer which is a raw material which has an unsaturated bond such as a group containing an active hydrogen and a double bond, and which is a raw material of the repeating unit represented by the above formula (1), can be represented by the above formula (2). It is produced by adding the polymerizable monomer of the raw material of the repeating unit and the polymerizable monomer other than the polymerizable monomer of the first functional group. A photopolymerization initiator or a thermal polymerization initiator may be used in the polymerization. Further, the same as the above can be used as the polymerizable monomer, the photopolymerization initiator, and the thermal polymerization initiator. Specific examples of the monomer having an active hydrogen-containing group and an unsaturated bond may be the above monomers. The polymer compound (D) has a polystyrene-equivalent weight average molecule of 323899 35 201246553, preferably 3,000 to 1,000 ooo, more preferably 5 to 5 Å, and may be linear or branched. Any one of the rings. The molar ratio of the polymerizable monomer which is a raw material of the ith functional group used in the molecular compound (D) to the monomer having an active hydrogen-containing group and an unsaturated bond is preferably 6 Å/ 1〇〇 to 15〇/1〇〇, more preferably 70/100 to 120/100, and even more preferably 90/100 to iio/ioo. If the molar ratio is less than 60/100 Å, the active hydrogen is excessive and the effect of reducing the hysteresis becomes small. When it exceeds 150/100, the excess of the functional group reactive with the active hydrogen increases the absolute value of the threshold voltage. Polymer compound (D) 'For example, poly(styrene-copolymer_[N-(3-mercaptopropenylmethoxypropyl-3',4'-didecylmaleimide)]-copolymerization -Amino-based ethylene-co-pentafluorostyrene-copolymer-[2-[〇-(Γ-mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly(styrene) -co-pentafluorostyrene-copolymerization||Ν-(3-mercaptopropenylmethoxypropyl-3',4'-dimercaptomaleimine)]-co-aminostyrene - copolymerization_[2_[ ι'_ (3',5'-diamidylpyrazolyl)carbonylamino]ethyl-methacrylate]), poly(styrene-co-pentafluorostyrene-copolymer -[Ν-(3-mercaptopropenylmethoxypropyl-3',4'-dimethylmaleimide)]-co-aminostyrene·co-acrylonitrile-copolymer-[2 -[0-(1,-decyl propyleneamino)carboxyamino]ethyl-methacrylate]), poly(.styrene-co-pentafluorostyrene-copolymer-[Ν- ( 3 - mercapto acryloyloxypropyl-3',4'-dimercaptomaleimine)]-co-aminostyrene-co-acrylonitrile-copolymer-[2-[ Γ- (3 ',5, two Pyrazolyl)carbonylamino]ethyl-mercapto acrylate]), poly(styrene-co-pentafluorostyrene-copolymer-[Ν-(3-mercaptopropenyloxypropyl 323899 36 8 201246553 . base_3,,4,-dimethylmaleimide)]-co-aminostyrene-co-acrylonitrile-copolymer-[2-[〇- 〇'-mercapto propyleneamine Base) ylamino]ethyl _. thiol acrylate]-co-allyl tridecyl fluorene), poly(styrene-copolymerization-• pentafluorostyrene-copolymer-[N-(3-A) Alkyl allyloxypropyl-1'-cyclohexene-1',2,-dimethylimine]]-co-aminostyrene-co-acrylonitrile-copolymer-[2-[ 1 ' - ( 3',5'-dimercapto "bisazolyl)carbonylamino]ethyl-mercapto acrylate]-co-allyl trimethyl fluorene], poly([Ν- (3-甲甲Acryl-yloxypropyl-1'-cyclohexenediimide)]-co-aminobenzene-bake-copolymerization of five gas styrene-copolymer-[2-[Ο- (1,- Mercaptopropylamino)carboxyamino]ethyl-mercapto acrylate]), poly([Ν-(3-methylpropenyloxypropyl-1'-cyclohexene dimethyl hydrazide) amine)]- Poly-aminostyrene-co-pentafluorostyrene-copolymer-[2-[ 1'-(3',5'-dimercapto "bisazolyl)carbonylamino]ethyl-mercapto acrylate ]), poly(aminostyrene-copolymerization) pentafluorostyrene-copolymer-[Ν-(3-mercaptopropenyloxypropyl-1'-cyclohexenediimide)] copolymerization -[2·[ 0-( 1,-decyl propyleneamino) sulfhydryl] ethyl decyl acrylate]), poly (amino styrene - copolymerization - pentafluoro styrene - copolymerization - [Ν-(3-Mercaptopropenyloxypropyl-1,-cyclohexene-1,2'-diimine)]-copolymerization_[2-[ 1,-(3,, 5,-Dimethylpyrazolyl)-monoaminomethyl]ethyl-mercaptopropionic acid]] and the like. <Reactive Nitrogen Compound (Ε) > The organic thin film transistor insulating layer material of the present invention may contain an active hydrogen compound (Ε). The active hydrogen compound (Ε) reacts with and bonds with the second functional group formed in the polymer compound (Α) to (D), whereby a crosslinked structure ❶ active hydrogen compound (Ε) can be formed inside the insulating layer. The invention includes a low molecular compound containing 2 323899 37 201246553 or more active hydrogens (hereinafter referred to as a low molecular weight active hydrogen compound (E-1)) and a polymer compound containing two or more active hydrogens (hereinafter referred to as a polymer active hydrogen compound (hereinafter referred to as a polymer active hydrogen compound ( E-2)). The active hydrogen typically exemplifies a hydrogen atom contained in an amine group, a hydroxyl group or a mercapto group. The active hydrogen is a reactive functional group as described above, and among them, hydrogen contained in a phenolic hydroxyl group which can be favorably reacted with an isocyanate group or an isothiocyanate group, hydrogen contained in an alcoholic group, and an aromatic amine group are preferable. Containing hydrogen. Specific examples of the low molecular weight active hydrogen compound (E-1) include a compound having a structure in which a group containing two or more active hydrogens is bonded to a low molecular structure. The low molecular structure may, for example, be an alkyl structure or a benzene ring structure. Specific examples of the low molecular compound include an amine compound, an alcohol compound, a phenol compound, and a thiol compound. In the present specification, the "alkyl structure" means a linear, branched or cyclic structure composed of an aliphatic hydrocarbon. On the other hand, the "benzene ring structure" means a linear, branched or cyclic structure composed of an aromatic hydrocarbon. Examples of the amine compound include ethylenediamine, propylenediamine, hexamethylenediamine, N,N,N',N',-tetraaminoethylethylenediamine, o-phenylenediamine, and m-benzene. Diamine, p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, melamine, 2,4,6-triaminopyrimidine, 1,5,9-triazacyclododecane, 1 , 3-bis(3-aminopropyl) tetradecyldioxane, 1,4-bis(3-aminopropyldimethylmethyl)benzene, 3-(2-aminoethylamine) The propyl group of tris(trimethyl sulphate) is calcined. Examples of the alcohol compound include ethylene glycol, 1,2-dihydroxypropane, glycerin, and 1,4-dioxanol. Examples of the phenolic compound include 1,2-dihydroxybenzene, 1,3-dihydroxy 323899 38 8 201246553 benzene, 1,4-dihydroxybenzene (hydroquinone), 1,2-dihydroxynaphthalene, isophthalic acid Resorcin, fluorinated glycerin, 2,3,4-tri-benzylic acid, 3,4,5-tri-benzylbenzamide. Examples of the thiol compound include ethanedithiol and terephthalic acid. A low molecular compound having two or more active argon, preferably an alcohol compound, a compound, or an aromatic amine compound. On the other hand, in the polymer active hydrogen compound (E-2), the active hydrogen may be bonded directly or via a specific group bond to the main chain constituting the polymer compound. Further, the active hydrogen may be contained in a structural unit constituting the polymer compound, and may be contained in each structural unit or may be contained only in a part of the structural unit. Further, the active hydrogen may be bonded only to the terminal of the polymer compound. Specific examples of the polymer active hydrogen compound (E-2) include compounds having a structure in which a group containing two or more active hydrogens is bonded to a polymer structure. The polymer-active cerium compound (E-2) can be obtained by forming a copolymer by separately polymerizing a monomer having an active hydrogen-containing group and an unsaturated bond such as a double bond; or Copolymerization of a polymerizable monomer which is a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2) or a repeating unit containing a first functional group; or copolymerization of the monomer with other monomers The compound is copolymerized. The polymerization or copolymerization of the polymerizable monomers is carried out by a method generally used by a related art. A photopolymerization initiator or a thermal polymerization initiator may be used in the polymerization. Further, the same as the above can be used as the polymerizable monomer, the photopolymerization initiator, and the thermal polymerization initiator. Specific examples of the monomer having an active hydrogen-containing group and an unsaturated bond can be exemplified by 323899 39 201246553. Among the monomers having an active hydrogen-containing group and an unsaturated bond, a monomer having an amine group is preferred. Further, as the polymer compound having two or more active hydrogens, a novolac resin obtained by condensing a compound with ruthenium in the presence of a catalyst is suitably used. The polymer compound having two or more active hydrogen-containing groups preferably has a polystyrene-equivalent weight average molecular weight of from 1 Torr to 1 Torr, more preferably from 3,000 to 500,000. Thereby, the effect of improving the flatness and uniformity of the insulating layer can be obtained. The weight average molecular weight in terms of polystyrene was determined by GPC. <Organic thin film transistor insulating layer material> Sigma 〇 〇;) to (4)) are both light and thermal energy crosslinkability, and can be used as the organic thin film transistor insulating (four) material of the present invention. The polymer compounds (4) and (8) do not have active hydrogen. However, the second functional group can be reacted with water by heating under moisture such as in the atmosphere, whereby the polymer compounds (A) and (B) can be thermally crosslinked. The preferred embodiment of the organic thin film transistor insulating layer material of the present invention contains high molecular weight. The composition of the substance (A) and/or (b) and the active hydrogen compound (e). The composition 's preferably contains a composition of the polymer compound (B) and the active nitride compound (E). Knife between. The mixing ratio of the substance (A) and/or (B) to the active hydrogen compound (E) is preferably such that the second functional group and the active hydrogen compound (8) which can be produced from the polymer compound (a) and/or (b) The activity of the towel contained 323899 40 201246553 The molar ratio of hydrogen to the base became 60/100 to 150/100. More preferably, it is made to have a ratio of 70/100 to 120/100, and more preferably it is a ratio of 90/100 to 110/100. If the molar ratio is less than 6〇/1〇〇, the excess of active hydrogen will reduce the effect of reducing the hysteresis. If it is mixed in a ratio of more than 150/100, the functional group reactive with reactive nitrogen Excessive will make the absolute value of the threshold voltage become larger. The organic thin film transistor blank material of the present invention is preferably a polymer compound (C). More preferably, the polymer compound (6) is a high molecular compound (D). Since the polymer compound (c) and the polymer compound (9) have a group containing a first functional group and an active hydrogen, they can be used alone in the organic thin film transistor insulating layer material of the present invention. The organic thin film transistor insulating layer material of the present invention contains an organic group and a functional group bonded to the polymer compounds (A) to (E). The content of the organic thin film transistor insulating layer material is considered, and the amount of the repeating unit having the organic group and the B group is adjusted, whereby the content of the organic functional group is appropriately determined. In a preferred aspect, the molar fraction of the repeating unit having the photodimerization reaction group is based on the total number of repeating units of the polymer compound contained in the organic thin film transistor insulating layer material. 〇〇1 to 七 and 0 05 to 06' are more preferably ο.1 to 〇·5. If the molar fraction of the photodimerization-based repeating unit is less than 〇〇1, there is a case where the hardening is not filled and the case exceeds 0.7, which adversely affects the crystal characteristics. The molar fraction of the weight of the first functional group is from 0.01 to 0.5, more preferably from 0.1 to 0.5. If the content of the first 323899 201246553 is 70, the mole rate is not reached. 1, there is a hardened and unfilled gas system mo·7 will have an adverse effect on the characteristics of the crystal; & good reaction with the 帛丨 functional group::: the total amount of the sub-compound, the introduction of high = object; More preferably, the mass is less than or equal to 5% by mass, more preferably from 1 to 4% by mass. If the amount of fluorine exceeds 50 mass 〆, the appearance of the material is deteriorated, and the affinity of the material is deteriorated, and the layer is difficult to be upper: and the organic thin film transistor insulating layer material which is mixed and bright may contain t. And to make a ruthenium molecule, such as a compound. The cross-linking agent can be used in combination with the cross-linking agent, and the solvent can be exemplified by tetra-nitrogen and diethyl sulphonate, etc., etc. A hydrocarbon solvent, an aromatic fumed solvent such as a butyl sulfonate, a sodium solvent such as acetone, a solvent solvent, an alcohol solvent such as isopropyl alcohol, a chloroform, etc. It is possible to use a leveling agent, a viscosity modifier, etc. which promotes the present invention. The organic thin film transistor and the insulating layer material are used for forming a composition of an insulating layer contained in the insulating body. The organic thin film transistor is organic thin, preferably used for forming an outer coating layer or a gate insulating layer. The layer is formed into a germanium crystal insulating layer material, preferably an organic thin film transistor outer coating machine thin organic thin film transistor More preferably, the gate insulating layer composition has a $electrocrystal||interpolar insulating layer material. The organic germanium transistor> the 1 m / 3238 figure shows that the bottom gate contact type of the embodiment of the present invention has 8 42 201246553 • Schematic cross-sectional view of the structure of the machine film transistor. The thin film transistor has a gate electrode 2 formed on the substrate 1 and a closed electrode layer formed on the gate electrode 2; 3. an organic semiconductor formed on the open insulating layer 3. The layer 4 is coated on the organic semiconductor layer 4 with the source electrode 5 and the electrodeless electrode 6 formed by the channel portion and the entire surface of the cover member. The bottom gate contact type organic thin film transistor can be, for example, It is manufactured by forming a gate electrode on a substrate, forming a spacer insulating layer on the dummy electrode, forming an organic semiconductor layer on the gate insulating layer, and forming a source electrode and a gate electrode on the organic semiconductor layer. Then, an outer coating is formed. The organic thin film transistor insulating layer material of the present invention is suitable for use as an organic thin film transistor opening insulating layer material for forming an interlayer insulating layer. Further, as an organic thin film transistor outer coating material It can be used for the formation of the outer coating layer. _ Fig. 2 is a schematic cross-sectional view showing the structure of the bottom gate bottom contact type organic thin germanium transistor of the present invention - the organic thin film transistor has the soil plate 1 a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, a source electrode 5 and a drain electrode 6 formed by sandwiching a channel portion on the gate insulating layer 3, The organic semiconductor layer 4 formed on the source electrode 5 and the electrodeless electrode 6 and the entire covering member are coated 7. The bottom gate bottom contact type organic thin film transistor can be manufactured, for example, by forming a via on the substrate. The electrode forms a boundary layer on the gate electrode, a source electrode and a electrodeless electrode are formed on the gate insulating layer, and an external coating is formed on the source electrode and the electrode electrode to form an organic semiconductor I'. The organic thin film transistor insulating layer material of the invention is suitable for forming an interlayer insulating layer as an organic thin film transistor gate insulating layer material. Further, 曰323899 201246553 can be used as an organic thin film transistor outer coating material. Coating shape

In the organic phase electro-crystal __ material according to its must-have solvent, etc., and the coating is applied to the surface of the layer under the outer layer or the outer coating layer and dried and hardened. Thereby, the formation of the layer or the outer coating layer is performed. The insulating layer (four) liquid used in the "^ If the organic layer_electrolytic layer material is dissolved, it is not particularly preferred for the point of pressure under normal pressure. C to fine. C organic solvent. Azaki Sa 3, son In the insulating layer coating liquid, two phases (fool point 151t) and propylene glycol monomethane (146t) e may be mentioned, depending on the necessary agent, surfactant, curing catalyst, etc. The organic layer rabbit of the present invention ^ The insulating layer material can be used as an organic thin film transistor gate insulating material and formed into a gate insulating layer. The insulating layer coating liquid can be formed by a known method such as plate printing or inkjet. The formed coating layer is dried. The solvent contained in the composition is removed. The spin coating method, the die coating method, and the net coating are applied to the gate electrode. It is necessary here to 'dry' refers to the coated resin adapter. The dried coating layer is hardened. The hardening refers to crosslinking the organic thin film electro-chemical layer material. The intersection of the dielectric insulating layer materials is performed, for example, by irradiating electromagnetic waves or applying heat by the two coating layers. The ith functional group of the compound (A) or (B) generates a second functional group, and the ^ a hydrogen-containing radical reaction of an energy-based free hydrogen compound (E). ί generates a second official base from the first functional group of the molecular compound (C) or (D) and makes the second official and molecular The reaction of the active hydrogen-containing group is contained. 323899 8 201246553 The intersection of the organic thin film transistor insulating layer material is performed by irradiating the coating layer with electromagnetic waves or electron beams. If the coating layer is irradiated with electromagnetic waves or electron beams, The cyclization reaction of the photodimerization reaction groups of the polymer compounds (A) to (8) is dimerized. The enthalpy functional groups contained in the molecular compounds (A) to (D) are generated by irradiation of electric wall waves. When the functional group of the second functional group reacts with the active hydrogen, the organic thin film transistor insulating layer is preferably formed by including a liquid containing a material of the organic thin germanium dielectric insulating layer on the substrate. a step of forming a coating layer thereon; and a method of forming a step of irradiating the coating layer with an electromagnetic wave or an electron beam. The ith functional group contained in the molecular compounds (A) to (D) is by heat When a functional group of a second functional group that reacts with active hydrogen is produced, The thin film transistor insulating layer preferably comprises the steps of: forming a coating layer on the substrate by applying a liquid containing the organic thin film transistor insulating layer material to the substrate; and irradiating the coating layer Forming a method of forming an electromagnetic wave or an electron beam. The organic thin film transistor insulating layer is preferably formed by coating a liquid containing an organic thin film transistor insulating layer material on a substrate. a step of coating the coating; irradiating the electromagnetic enthalpy or the electron beam; and forming a thermal step on the coating layer. This is because the electromagnetic wave or electron beam is irradiated to the coating layer. The step and the step of applying heat to the coating layer increase the crosslink density of the insulating layer. Especially when the organic thin film transistor insulating layer material is used in the gate electrode layer, the threshold voltage of the organic thin film transistor is lowered. (vth) Absolute value and hysteresis 45 323 201246553 Post-phenomenon" This is considered to increase the polarization of the applied voltage and increase the threshold voltage of the organic thin film transistor by increasing the crosslink density of the insulating layer. Absolute pressure and hysteresis. When heat is applied to the coating layer, the coating layer is heated at a temperature of from about 80 to 250 ° C, preferably from about 100 to 230 ° C, for about 5 to 120 minutes, preferably from about 1 to 60 minutes. . If the heating temperature is too low or the heating time is too short, the crosslinking of the insulating layer may be insufficient. If the heating temperature is too high or the heating time is too long, the insulating layer may be damaged. When the coating layer is irradiated with electromagnetic waves, the irradiation conditions are adjusted in consideration of the crosslinking of the insulating layer and the degree of damage. When microwaves are applied and heated, the heating conditions are adjusted in consideration of the crosslinking of the insulating layer and the degree of damage. The wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 150 to 410 nm. If the wavelength of the electromagnetic wave to be irradiated exceeds 450 nm, the crosslinking of the organic thin film dielectric insulating layer material may be insufficient. The electromagnetic wave is preferably ultraviolet light. The irradiation of ultraviolet rays can be carried out, for example, by using an exposure device used for manufacturing a semiconductor and a UV lamp used for curing a UV curable resin. Irradiation of the electron beam can be performed, for example, using an ultra-small electron beam irradiation tube. Heating can be carried out using a heater, an oven, or the like. Other irradiation conditions and heating conditions are appropriately determined depending on the type and amount of the photodimerization reaction group. A self-organized monomolecular film layer can be formed on the gate insulating layer. The self-assembled monomolecular film layer can be formed, for example, by dissolving 1 to 1% by weight of an alkylchlorodecane compound or an alkyl alkoxydecane compound t solution in an organic solvent for treating a gate insulating layer. Examples of the calcined base gas smoldering compound include methyl triphosite, Bhd. 323899 46 8 201246553-trichlorodecane, butyl trichlorodecane, decyltrichlorodecane, and octadecyltrichlorodecane. Examples of the alkyl alkoxydecane compound include mercaptotrimethoxydecane, ethyltrimethoxydecane, butyltrimethoxydecane, decyltrimethoxyxanthene, and octadecyltrimethoxysilane. Xiyuan. The substrate 1, the gate electrode 2, the source electrode 5, the drain electrode 6, and the organic semiconductor layer 4 can be formed using commonly used materials and methods. As the material of the substrate, a resin or plastic plate or film, a glass plate, a fascia, or the like can be used. The electrode is made of chromium, gold, silver, aluminum, molybdenum or the like, and is formed by a known method such as a steaming method, a sputtering method, a printing method, or an inkjet method. As the organic semiconductor compound for forming the organic semiconductor layer 4, a 7-inch total polymer is used, and for example, polypyrroles, polythiophenes, polyanilines, polyallylamines, anthracenes, polycarbazoles, poly Terpenoids, poly(p-phenylene vinyl) and the like. Further, as a low molecular substance having solubility in an organic solvent, for example, a polycyclic aromatic derivative such as fused pentene, a phthalocyanin derivative, a perylene derivative, or a tetrathiafulvalene derivative may be used. , tetracyanoquinodimethane derivatives, fullerenes, carbon nanotubes, and the like. Specific examples thereof include 2,1,3-benzothiadiazole-4,7-di(ethyl borate) and 2,6-dibromo-(4,4-bis-hexadecyl-411- a condensate of cyclopenta[2,lb; 3,4-b']-dithiophene, 9,9-di-n-octyl-2,7-di(ethyl borate) and 5,5'-di a condensate of bromine-2,2'-bisthiophene, etc. For example, a solvent may be added as necessary to prepare an organic semiconductor coating solution and the organic semiconductor coating liquid is applied to 323899 47 201246553 In the insulating layer, the organic semiconductor coating liquid is dried, whereby the organic semiconductor layer is formed. In the present invention, the resin constituting the gate insulating layer has a benzene ring and has affinity with an organic semiconductor compound. By the coating drying method, a uniform and flat interface can be formed between the organic semiconductor layer and the gate insulating layer. The solvent used in the organic semiconductor coating liquid is not particularly limited as long as it can dissolve or disperse the organic semiconductor. It is preferably a solvent having a boiling point of from 50 to 20 (TC) at normal pressure. Examples of the solvent include: gas, toluene, benzyl ether 2-heptanone and propylene glycol monoterpene ether acetate. The organic semiconductor coating liquid can be a known method such as a spin coating method, a die coating method, screen printing, or inkjet, similarly to the above-described insulating layer coating liquid. The organic thin film transistor of the present invention can be used for the purpose of protecting the organic thin film transistor, and is coated with an outer coating material for the purpose of improving surface smoothness. An insulating layer made of a crystalline insulating layer material may have a flat film or the like laminated thereon, and a laminated structure may be easily formed. Further, an organic electroluminescent device may be suitably mounted on the insulating layer. The organic thin film of the present invention is used. The material of the transistor insulating layer can be used for a display member having an organic thin film transistor. The display member having the organic thin film transistor can be used to manufacture a display having a member for display. The organic thin film transistor insulating layer of the present invention The material can be used for forming a layer contained in a transistor other than the insulating layer and forming a layer contained in the organic electroluminescent element. 3899 48 8 201246553 - (Embodiment) Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the actual embodiment, and there is no need for rumors. [Synthesis Example 1] (Synthesis of Compound 1) Into a 500 ml eggplant type flask with a water trap and stirrer, add 1-cyclohexan-1,2-diacid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 25 g, 3-aminopropanol 12 g The toluene was reacted for 200 hours in an oil bath at 140 ° C for 4 hours. After the reaction was completed, the reaction mixture was shaken by a rotary evaporator, and 100 ml of diethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The obtained diethyl ether solution was transferred to a separatory funnel, and after washing with an aqueous solution of sodium carbonate, the aqueous layer was washed with water until neutral, and liquid separation was carried out. After the organic layer was dried over anhydrous magnesium sulfate, the solid was filtered, and the filtrate was concentrated on a rotary evaporator to afford compound 1 as a tan, viscous liquid. 〇

(Synthesis of Compound 2) In a 1 L three-necked flask equipped with a three-way stopcock, compound 16.26 g, thioglycol 11.31 g, N,N,-dicyclohexylcarbodiimide (and pure light) were added. Pharmacopoeia 27.10 g, a catalytic amount of 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 1,4-dioxane 400 ml, and stirred under a nitrogen atmosphere of 323899 49 201246553 for 24 hours and reacted. After the completion of the reaction, the precipitate was filtered, and the filtrate was concentrated on a rotary evaporator, and 100 ml of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The obtained diethyl ether solution was transferred to a separatory funnel, washed with an aqueous solution of sodium carbonate, and then the aqueous layer was washed with water until neutral. After the organic layer was dried over anhydrous magnesium sulfate, the solid was filtered, and the filtrate was concentrated on a rotary evaporator to afford compound 2 as a yellowish brown viscous liquid.

Compound 2 (Synthesis of Polymer Compound 3) 2.50 g of 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) and aminostyrene (Tokyo Chemical Co., Ltd.) were placed in a 50 ml pressure vessel (made by Ace). 0.82 g, 2-(0-[1'-mercaptopropylamino)carboxyamino)ethyl-methacrylic acid vinegar (manufactured by Showa Denko, trade name "Karenz MOI-BM") 1.65 g, 2.86 g of compound 2,2,2'-azobis(2-mercaptopropionitrile) 0.04 g, propylene glycol monoterpene ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 17.17 g, and bubbling with argon gas After the dense bolt. The polymerization was carried out in an oil bath of 60 ° C for 20 hours to obtain a viscous propylene glycol monoterpene ether acetate solution in which the polymer compound 3 was dissolved. The polymer compound 3 has the following repeating unit. The number next to the brackets indicates the molar fraction of the repeating unit. 323899 50 8 201246553

The polymer compound 3 obtained from the polymer compound 3 had a weight average molecular weight of 50,000 (standard GPC, Tskgel SUperHM H i branch + Tskgel super H2000 1 , mobile phase = THF). [Synthesis Example 2] (Synthesis of Polymer Compound 4) 1.88 g and 2,6-dibromo-(4) containing 2,1,3-benzothiadiazole-4,7-di(ethyl borate) , 4-bis-hexadecyl-411-cyclopenta[2,1-13;3,4-13']-diphenanthene 3.8 lg of benzene (80 ml), added four (three stupid) under nitrogen 0.75 g of palladium), gasified decyltrioctylammonium (trade name "Aliquat 336" (5 major book mark) manufactured by Aldrich), 〇g, and 2 ml of 2M aqueous sodium carbonate solution. The mixture was vigorously stirred and The mixture was heated and refluxed for 24 hours. The viscous reaction mixture was poured into 500 ml of acetone to precipitate a fibrous yellow polymer. The polymer was collected by filtration and washed with acetone, and dried at 60 ° C for one night in a vacuum oven. The obtained polymer is referred to as a polymer compound 323899 51 201246553 4. The polymer compound 4 has the following repeating unit. η represents the number of repeating units 0

Polymer Compound 4 Polymer Compound 4 has a weight average molecular weight of 32,000 from standard polystyrene (GPC, Tskgel super ΗΜ-Η 1 branch + Tskgelsuper H2000 1 branch, mobile phase = THF) 0 [Example 1 (Production of organic thin film transistor insulating layer material and electric field effect type organic thin film transistor) In a 10 ml sample vial, 2.00 g of propylene glycol monoterpene ether acetate solution of the polymer compound 3 obtained in Synthesis Example 1 was added, and propylene glycol was added. Methyl ether acetate (2.00 g) was simultaneously dissolved while stirring, and was prepared into a uniform coating solution 1 of an organic thin film transistor insulating layer material. The obtained coating solution was filtered using a membrane filter having a pore size of 0.2 / zm, and applied to a glass substrate containing a chromium electrode by a spin coating method, followed by drying at 100 ° C for 1 minute on a hot plate. Thereafter, it was irradiated with UV light (wavelength 365 nm) of i6 〇〇mJ/cm 2 using an aligner (manufactured by Canon, PLA-521), and then fired at 2 〇〇C on a hot plate in nitrogen gas. 0 minute and obtain the interlayer insulation layer. Next, the polymer compound 4 was dissolved in diphenylbenzene in a solvent to prepare 52 323899 8 201246553 as a solution (organic semiconductor composition) having a concentration of 0.5% by weight, which was filtered by a membrane filter to prepare a coating liquid. . The resulting coating liquid is applied onto the gate insulating layer by spin coating to form an active layer having a thickness of about 30 nm, followed by vacuum evaporation using a metal mask. On the active layer, a source electrode having a channel length of 20 nm and a channel width of 2 mm and a electrodeless electrode (having a laminated structure in the order of indium oxide and gold from the active layer side) are formed, thereby producing an electric field effect type organic film. Transistor. <Evaluation of Transistor Characteristics> The electric field effect type organic thin film transistor thus produced is such that the gate voltage Vg is changed to 20 to -40 V, and the source/drain voltage Vsd is changed to 0 to -40 V. 'The crystal characteristics were measured using a vacuum probe (BCT22MDC-5-HT-SCU; manufactured by Nagase Electronic Equipments Service Co., LTD.). The result is shown in the hysteresis phenomenon of the electric field effect type organic thin film transistor. The source/drain voltage Vsd is -40V, and the threshold voltage Vthl and the gate voltage Vg when the gate voltage Vg changes to 20V-►MOV is changed to The voltage difference of the threshold voltage Vth2 at -40V - 20V is expressed. [Comparative Example 1] (Manufacture of electric field effect type organic thin film transistor) In a 10 ml sample vial, polyvinyl phenol-co-poly(decyl methacrylate) (manufactured by Aldrich, Mn = 6700) was added. n,N,N',N,,N,,,N,'-hexamethoxy decyl melamine (manufactured by Sumitomo Chemical Co., Ltd.) 0.163 g, thermal acid generator (Midori Chemical Co., Ltd., trade name: TAZ-108 0.113 g, 323899 53 201246553 2-heptanone 7.00 g, dissolved and dissolved to prepare a uniform coating solution 2. An electric field effect type organic thin film transistor was produced in the same manner as in Example 1 except that the coating solution 1 was used instead of the coating solution 1, and UV irradiation was not performed when the gate insulating layer was formed. The transistor characteristics were measured. When evaluated, the gate voltage Vg did not operate as a transistor in the region of 20 V to -40 V. [Table 1] Threshold voltage Vth 1 Example 1 0.0 V -6, 4 V Comparative Example 1 No operation [Fig. 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 cross-sectional view showing the structure of a bottom gate contact type organic thin film transistor according to another embodiment of the present invention. [Main component symbol description] 1 Substrate 2 Gate electrode 3 Gate insulating layer 4 Organic semiconductor layer 5 Source electrode 6 〉 and pole electrode 7 Overcoat 323899 54

Claims (1)

201246553 VII. Patent application scope: 1. An organic thin film transistor insulating layer material containing a polymer compound (A) 'The polymer compound (a) has a repeating unit represented by the formula (丨) and contains a first functional group a repeating unit, wherein the ith 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; (1) [wherein the ruler 2 represents a hydrogen atom or a fluorenyl group; and Rs and R4 each independently represent a one-valent organic group having 1 to 20 carbon atoms; the nitrogen atom in the monovalent organic group may be substituted by a fluorine atom, & a carbon atom may be bonded to a carbon atom to form a 5-membered ring or a 6-membered ring; 'indicating a main chain and a side chain linking the polymer compound, and may have a linking moiety of a fluorine atom; ^ means 〇 or 1 Integer]. 2. The organic thin film transistor insulating layer material according to the above application, wherein the polymer compound (A) has a repeating unit represented by the formula (2); 323899 201246553 (Rf)b (2) [wherein, Ri represents a hydrogen atom or a fluorenyl group; R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; and Rf represents a fluorine atom or a carbon number of 1 to 20 having a fluorine atom; a monovalent organic group; Raa represents a main chain and a side chain of a linking polymer compound, and may have a linking moiety of a fluorine atom; u represents an integer of 0 or 1, and b represents an integer of 1 to 5; when R is plural, The same may or may not be the same; when Rf is plural, the terms may be the same or different]. 3. The organic thin film transistor insulating layer material according to claim 1 or 2, wherein the first functional group is blocked by an isocyanate group blocked by a blocking agent, and blocked. At least one group selected from the group consisting of isothiocyanato blocked by the agent. 4. The organic thin film transistor insulating layer material according to claim 3, wherein the isocyanate group blocked by the blocker and the isothiocyanate group blocked by the blocker (3) the base represented; [wherein, Xa represents an oxygen atom or a sulfur atom, and R5 and R6 are the same or different, and 2 323899 8 201246553 represents a hydrogen atom or a carbon number of 1 to 20 one-valent organic group]. 5. The organic thin film transistor insulating layer material as described in claim 3, wherein the isocyanate group blocked by the blocker and the isothiocyanate blocked by the blocking agent a group represented by the formula (4); H ib /N^R7 —N—C—N (4) [wherein Xb represents an oxygen atom or a sulfur atom, and the heart is the same or different, representing a hydrogen atom or Carbon number 1 to 20 one-valent organic group]. The organic thin film transistor insulating layer material according to any one of the above-mentioned claims, wherein the polymer compound (a) is contained in two or more! The structure of one active hydrogen has two or more structural units of active hydrogen. + ^❹ 7. If you apply for a patent scope! The organic thin film transistor insulating layer material according to any one of the above-mentioned items, comprising an active hydrogen compound having a low molecular compound having two or more active hydrogens, and a polymer compound having two or more active hydrogens At least one active hydrogen compound selected from the group consisting of hydrogen compounds. L A method for forming an organic thin film transistor insulating layer, comprising: will contain the scope as claimed in the patent! a step of coating a liquid of an organic thin film transistor insulating layer material according to any one of the items 7 onto a substrate, forming a coating layer on the substrate; and irradiating the coating layer with an electromagnetic wave or an electron beam . 323899 3 201246553 9· A method for forming an organic thin germanium transistor insulating layer, comprising: coating a liquid containing an organic thin film transistor insulating layer material according to any one of claims 1 to 7 a step of forming a coating layer on the substrate; a step of irradiating the coating layer with an electromagnetic wave or an electron beam; and a step of applying heat to the coating layer. The method for forming an organic thin film dielectric insulating layer according to the invention of claim 8 or claim 9, wherein the electromagnetic wave is ultraviolet light. An organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material according to any one of claims 1 to 7. 12. The organic thin film transistor according to the invention of claim U, wherein the organic thin film transistor insulating layer is a gate insulating layer. A display member comprising the organic thin film transistor according to the above-mentioned item or item 12 of the patent application. 14. A display comprising the display described in claim 13 323899 8 4