JP2013064095A - Organic thin-film transistor insulating layer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin-film transistor insulating layer material that can manufacture organic thin-film transistors in which the absolute value of the threshold voltage and hysterisis are small.SOLUTION: The present invention is an organic thin-film transistor insulating material containing: (A) a polymer compound containing a repeating unit that contains a first functional group in a molecule, wherein the first functional group can produce a second functional group capable of reacting with active hydrogen, through the effects of heat or electromagnetic wave irradiation; and an active hydrogen compound (B) containing a divalent organic group and two or more active hydrogen in a molecule, wherein the divalent organic group has a structure such that a disubstituted carbylene group is bonded to an oxycarbonyloxylene group.

Description

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

  Since an organic thin film transistor can be manufactured at a lower temperature than an inorganic semiconductor, a plastic substrate or a film can be used as the substrate. By using such a substrate, an element that is flexible, lightweight, and hardly broken can be obtained. In some cases, an element can be manufactured by application of a solution containing an organic material or film formation using a printing method, and a large number of elements can be manufactured on a large-area substrate at low cost.

  In addition, since there are a wide variety of materials that can be used for studying transistors, if materials having different molecular structures are used for studying, elements having a wide range of characteristics can be manufactured.

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

  In addition, the organic semiconductor compound used for the organic semiconductor layer of the field effect organic thin film transistor is easily affected by the environment such as humidity and oxygen, and the transistor characteristics are likely to deteriorate over time due to humidity and oxygen.

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

  Thus, in the organic thin film transistor, an insulating layer material is used to form an overcoat insulating layer, a gate insulating layer, and the like that cover the organic semiconductor layer. In the present specification, an insulating layer or an insulating film of an organic thin film transistor such as the overcoat insulating layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer. A material used for forming the organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material.

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

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

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

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

  Patent Document 2 describes a resin composition for an organic thin film transistor gate insulating layer that contains fluorine and prevents the polarization of the organic thin film transistor gate insulating layer by forming a cross-linked structure, thereby reducing the hysteresis of the organic thin film transistor. .

JP2007-305950A JP 2011-38062 A

Appl. Phys. Lett. 89,093507 (2006) Appl. Phys. Lett. 92, 183306 (2008)

  However, in consideration of practical use of a light-emitting element such as an organic electroluminescence element (organic EL element), it is necessary to further improve the operation accuracy of the organic thin film transistor. Therefore, there is a demand for an organic thin film transistor insulating layer material that can reduce the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor.

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

  In view of the above, the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor can be reduced by forming the gate insulating layer using a specific resin composition capable of forming a crosslinked structure.

  That is, the present invention relates to a polymer compound (A) containing a repeating unit containing the following first functional group in the molecule,

（１）

(1)

[Wherein, R ₁ and R ₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ]
An organic thin film transistor insulating layer material comprising an active hydrogen compound (B) containing a divalent organic group represented by formula (2) and two or more active hydrogens;
First functional group: a functional group capable of generating a second functional group capable of reacting with active hydrogen by the irradiation of electromagnetic waves or the action of heat.
Is to provide.

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

（２）

(2)

[Wherein R ₃ represents a hydrogen atom or a methyl group. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. R represents an organic group that can be removed by an acid. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. a represents an integer of 0 or 1, and n1 represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of R ′, they may be the same or different. ]
It is a high molecular compound (A-1) containing the repeating unit represented by these.

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

（３）

(3)

[Wherein, R ₄ represents a hydrogen atom or a methyl group. R ₅ and R ₆ represent a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _bb represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. b represents an integer of 0 or 1, and n2 represents an integer of 1 to 5. When there are a plurality of R ₅ , they may be the same or different. When there are a plurality of R _{6 s} , they may be the same or different. When there are a plurality of R ″, they may be the same or different. ]
It is a high molecular compound (A-2) containing the repeating unit represented by these.

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

（４）

(4)

[Wherein, R ₇ represents a hydrogen atom or a methyl group. R _cc represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. c represents an integer of 0 or 1. ]
The repeating unit represented by

（５）

(5)

[Wherein R ₈ represents a hydrogen atom or a methyl group. R ′ ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _dd represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. d represents an integer of 0 or 1. m represents an integer of 1 to 5. When there are a plurality of R ′ ″, they may be the same or different. ]
It is a high molecular compound (A-3) containing the at least 1 sort (s) of repeating unit chosen from the group which consists of a repeating unit represented by these.

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

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

（６）

(6)

[Wherein, Xa represents an oxygen atom or a sulfur atom, and R ₉ and R ₁₀ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

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

（７）

(7)

[Wherein, Xb represents an oxygen atom or a sulfur atom, and R _{11 to} R ₁₃ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

  In one certain form, the said active hydrogen compound (B) is a formula.

（８）

(8)

[Wherein, R _{14 to} R ₂₁ and R _{26 to} R ₃₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _{22 to} R ₂₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _aaa , R _bbb and R _ccc each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. X ₁ and X ₂ each independently represent an amino group, a substituted amino group, a hydroxyl group or a thiol group. p1, p2 and p3 each independently represents an integer of 0 or 1. ]
It is an active hydrogen compound represented by these.

  In one certain form, it further contains the unsaturated double bond compound (C) which has a 2 or more unsaturated double bond in a molecule | numerator.

  In one certain form, the said unsaturated double bond compound (C) is a formula.

（９）

(9)

[Wherein, R _{34 to} R ₃₈ and R _{43 to} R ₄₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _{39 to} R ₄₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _ddd, R _eee and _{R fff} each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. p4, p5 and p6 each independently represent an integer of 0 or 1. ]
It is an unsaturated double bond compound represented by these.

  Moreover, this invention provides the organic thin-film transistor which has the organic thin-film transistor insulating layer formed using the said organic thin-film transistor insulating-layer material.

  In one certain form, the said organic thin-film transistor insulating layer is a gate insulating layer.

  Moreover, this invention provides the member for a display containing the said organic thin-film transistor.

  Moreover, this invention provides the display containing the said member for a display.

  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 low absolute value of threshold voltage and a low hysteresis.

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

  In the present specification, the “polymer compound” refers to a compound containing a structure in which a plurality of the same structural units are repeated in the molecule, and includes a so-called dimer.

  The organic thin film transistor insulating layer material of the present invention comprises a polymer compound (A) having a plurality of functional groups that react with active hydrogen when electromagnetic waves or heat is applied, and a di-substituted carbylene group in the oxycarbonyloxylene group in the molecule. An active hydrogen compound (B) having a divalent organic group having a bonded structure and a plurality of active hydrogens is contained. Active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom, a nitrogen atom and a sulfur atom.

<Polymer Compound (A)>
The organic thin film transistor insulating layer material of the present invention contains a polymer compound (A), the polymer compound (A) has a plurality of first functional groups, and the first functional groups react with active hydrogen. The second functional group that can be generated is a functional group that can be generated by the irradiation of electromagnetic waves or the action of heat.

  The first functional group contained in the polymer compound (A) does not react with active hydrogen. However, when the first functional group is irradiated with electromagnetic waves or heat, the second functional group is generated, and the second functional group is generated. The functional group reacts with active hydrogen. That is, the first functional group is deprotected by electromagnetic wave irradiation or heat action to generate a second functional group that can react with active hydrogen. The second functional group reacts with and binds to the active hydrogen of the active hydrogen compound (B), so that a crosslinked structure can be formed inside the insulating layer.

  When a crosslinked structure is formed inside the organic thin film transistor insulating layer, the movement of the molecular structure is suppressed, and the polarization of the insulating layer is suppressed. When the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the absolute value of the threshold voltage of the organic thin film transistor is lowered, and the operation accuracy is improved.

  The second functional group is protected (blocked) until the electromagnetic wave is irradiated or heat is applied in the step of forming the insulating layer of the organic thin film transistor. In the organic thin film transistor insulating layer material, the second functional group is protected. Exists. As a result, the storage stability of the organic thin film transistor insulating layer material is improved.

  Preferable examples of the first functional group include an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent.

  The isocyanato group blocked with the blocking agent can be produced by reacting an isocyanato group with a blocking agent having only one active hydrogen capable of reacting with the isocyanato group in one molecule. The isothiocyanate group blocked with the blocking agent can be produced by reacting a blocking agent having only one active hydrogen capable of reacting with the isothiocyanato group in one molecule with the isothiocyanato group.

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

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

  Examples of the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent that may be used in the present invention include the group represented by the formula (6) and the formula (7). Are preferred.

  In a preferred embodiment, the polymer compound (A) contains both a group represented by the formula (6) and a group represented by the formula (7). The group represented by the formula (6) and the group represented by the formula (7) have different reactivity, and when the polymer compound (A) contains both, the curing may be performed stepwise. , It becomes possible to select a functional group to be reacted.

In Formula (6) and Formula (7), Xa represents an oxygen atom or a sulfur atom, Xb represents an oxygen atom or a sulfur atom, and R _{9 to} R ₁₃ each independently represent a hydrogen atom or a carbon number of 1 Represents a monovalent organic group of ˜20.
The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be saturated or unsaturated.
Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon having 3 to 20 carbon atoms. Groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as straight chain hydrocarbon groups having 1 to 6 carbon atoms, branched hydrocarbon groups having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. A cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferred.
The straight chain hydrocarbon group having 1 to 20 carbon atoms, the branched hydrocarbon group having 3 to 20 carbon atoms, and the cyclic hydrocarbon group having 3 to 20 carbon atoms are such that the hydrogen atoms contained in these groups are fluorine atoms. May be substituted.
In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

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

In one certain form, R < ₉ > is a methyl group, R < ₁₀ > is an ethyl group, and R < ₁₁ > -R < ₁₃ > is a hydrogen atom.

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

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

  One preferable aspect of the high molecular compound (A) used for this invention is a high molecular compound (A-1) containing the repeating unit represented by the said Formula (2) further.

In formula (2), R ₃ represents a hydrogen atom or a methyl group. In some one aspect, R ₃ is a methyl group.

In formula (2), R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be saturated or unsaturated.
Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon having 3 to 20 carbon atoms. Groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as straight chain hydrocarbon groups having 1 to 6 carbon atoms, branched hydrocarbon groups having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. A cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferred.
In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with an alkyl group, a chlorine atom, a bromine atom, an iodine atom, or the like.

Specific examples of the monovalent organic group having 1 to 20 carbon atoms which may be substituted with a fluorine atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, Tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthryl, tolyl, xylyl Group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, ethenylnaphthyl group, methyl Anthryl group Ethyl anthryl group, chlorophenyl group, and, bromo phenyl group.
As the monovalent organic group having 1 to 20 carbon atoms, an alkyl group is preferable.

  In one certain form, R 'is a hydrogen atom.

  In formula (2), R represents an organic group that can be removed by the action of an acid. The organic group that can be eliminated by an acid is preferably an organic group that can be eliminated by the action of an acid to produce a phenolic hydroxyl group. The phenolic hydroxyl group can react with the second functional group to form a crosslinked structure. Examples of the organic group that can be eliminated by the acid include a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a 2-ethoxyethyl group, a tetrahydropyranyl group, a cyclopropylmethyl group, and a cyclohexyl group. It is done.

  In formula (2), n1 represents the integer of 1-5. In one certain form, n1 is 1.

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

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

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

  Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms that may be substituted with an alkyl group or the like include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.

  Another preferable embodiment of the polymer compound (A) used in the present invention is a polymer compound (A-2) further containing a repeating unit represented by the formula (3).

The dithiocarbamylmethylphenyl group (—Ph—CH ₂ —SCSNR ₅ R ₆ ) substituted with R ₅ and R ₆ contained in the polymer compound (A-2) is converted into a benzyl radical by the irradiation of electromagnetic waves or the action of heat. Is generated. The benzyl radical can form a carbon-carbon bond by radical coupling. Therefore, the polymer compound (A-2) can form a crosslinked structure inside the insulating layer. Benzyl radicals can also initiate radical polymerization of compounds having unsaturated double bonds. Therefore, when the organic thin film transistor insulating layer material contains a compound having an unsaturated double bond, a crosslinked structure can be formed inside the insulating layer.

In formula (3), R ₄ represents a hydrogen atom or a methyl group. In some one aspect, R ₄ is hydrogen atom.

In formula (3), R ₅ and R ₆ each independently represent a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₅ and R ₆ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by the aforementioned R ′. Same as example. In some one aspect, _{R 5} and _{R 6} is an ethyl group.

In formula (3), R _bb represents a linking moiety that links the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. The definition and specific examples of the linking moiety represented by R _bb are the same as the definition and specific examples of the linking moiety represented by R _aa described above.
b represents an integer of 0 or 1. In one certain form, b is 0.

  In formula (3), R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ″ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ described above. The same. In one certain form, R '' is a hydrogen atom.

  In formula (3), n2 represents the integer of 1-5. In one certain form, n2 is 1.

  A preferred embodiment of the polymer compound (A-2) used in the present invention is at least selected from the group consisting of the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5). This is a polymer compound (A-3) containing one type of repeating unit.

  The terminal unsaturated double bond contained in the polymer compound (A-3) reacts with a benzyl radical provided by the polymer compound (A-2) to polymerize, for example. At that time, the radical reaction proceeds in parallel with the reaction between the second functional group and active hydrogen, and the crosslink density of the organic thin film transistor insulating layer material is effectively increased.

In formula (4), R ₇ represents a hydrogen atom or a methyl group. In some one aspect, R ₇ is a methyl group.

In formula (4), R _cc represents a linking moiety that links the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. The definition and specific examples of the connecting part represented by R _cc are the same as the definition and specific examples of the connecting part represented by R _aa described above. In one form, R _cc is a bond represented by —COO—CH ₂ CH ₂ —.
c represents an integer of 0 or 1. In one certain form, c is 1.

In formula (5), R ₈ represents a hydrogen atom or a methyl group. In some one aspect, R ₈ is methyl group.

In formula (5), R _dd represents a linking moiety that links the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. The definition and specific examples of the connecting part represented by R _dd are the same as the definition and specific examples of the connecting part represented by R _aa described above. In one certain form, R _dd is a bond represented by —COO—CH ₂ CH ₂ —NH—CO—NH—.
c represents an integer of 0 or 1. In one certain form, c is 1.

  In formula (5), m represents an integer of 1 to 5. In one certain form, m is 1.

  In formula (5), R ′ ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ ″ are the definitions and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ described above. Is the same. In one certain form, R '' 'is a hydrogen atom.

  The polymer compound (A) can be produced, for example, by a method of polymerizing a polymerizable monomer containing the first functional group using a photopolymerization initiator or a thermal polymerization initiator.

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

  Examples of the compound having an unsaturated double bond and an isocyanato group in the molecule include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl isocyanate. Can be mentioned. Examples of the compound having an unsaturated double bond and an isothiocyanato group in the molecule include 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl. An isothiocyanate is mentioned.

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

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

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

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

  The thermal polymerization initiator may be any compound that serves as a radical polymerization initiator. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylpropane) ), Azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyl peroxide Oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxy , Diacyl peroxides such as o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide Hydroperoxides such as oxide, tert-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, tris (tert-butylperoxy) triazine 1,1-di-tert-butylperoxycyclohexane, peroxyketals such as 2,2-di (tert-butylperoxy) butane, tert-butylperoxypivalate, tert-butylperoxy 2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3,5,5-trimethyl Alkyl peresters such as hexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-butyl peroxytrimethyladipate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, Examples include peroxycarbonates such as tert-butylperoxyisopropyl carbonate.

  The polymer compound (A-1) includes, for example, a polymerizable monomer containing a first functional group and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (2), as a photopolymerization initiator or heat. It can manufacture by the method of copolymerizing using a polymerization initiator.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (2) include 4- (1-ethoxyethoxy) styrene, 4-tertiary butoxystyrene, and 2-ethyl-2-adamantyloxy- Methacrylate is mentioned.

  The polymer compound (A-2) includes, for example, a polymerizable monomer containing a first functional group and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (3), as a photopolymerization initiator or heat. It can manufacture by the method of copolymerizing using a polymerization initiator.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) include N, N-diethyldithiocarbamylmethylstyrene.

  In addition, the polymer compound (A-2) has a formula instead of a polymerizable monomer that is a raw material of the repeating unit represented by the formula (3).

[Wherein, R ″, R ₄ , R _bb , b and n2 are as defined above, and X is a halogen atom. ]
The monomer mixture may be copolymerized in the same manner as described above except that a polymerizable monomer having a structure represented by the following formula is used, and then reacted with a metal salt of N, N-dialkylthiocarbamic acid. Good.

  Examples of polymerizable monomers having active hydrogen in the molecule include acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, acrylic acid-3-hydroxypropyl, acrylic acid-2-hydroxybutyl, and acrylic acid-4- Hydroxyphenyl, acrylic acid-2-hydroxyphenylethyl 2-aminoethyl methacrylate, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-2 -Hydroxybutyl, methacrylic acid-4-hydroxyphenyl, methacrylic acid-2-hydroxyphenylethyl, 4-aminostyrene, 4-allylaniline, 4-aminophenyl vinyl ether, 4- (N-phenylamino) phenyl allyl ether 4 (N- methylamino) phenyl allyl ether, 4-aminophenyl allyl ether, allylamine, 2-aminoethyl acrylate, 4-hydroxystyrene, and include 4-hydroxy-allyl benzene.

  The polymer compound (A-3) is, for example, a polymerizable monomer containing a first functional group, a polymerizable monomer that is a raw material for the repeating unit represented by the formula (3), and a polymer having active hydrogen in the molecule. Is produced by a method in which a functional monomer is copolymerized using a photopolymerization initiator or a thermal polymerization initiator and then reacted with a compound containing a functional group that reacts with active hydrogen and an unsaturated double bond in the molecule. I can do it.

  Compounds containing a functional group that reacts with active hydrogen in the molecule and an unsaturated double bond include acryloyl chloride, methacryloyl chloride, acrylic anhydride, methacrylic anhydride, 2-isocyanatoethyl acrylate, 2-isocyanate. Examples include natoethyl methacrylate, 4-vinylbenzoyl chloride, and 4-vinylphenyl isocyanate.

  In the production of the polymer compound (A), the polymer compound (A-1), the polymer compound (A-2) and the polymer compound (A-3), a polymerizable monomer containing the first functional group, Polymerizable monomer other than the polymerizable monomer that is a raw material of the repeating unit represented by formula (2), the polymerizable monomer that is the raw material of the repeating unit represented by formula (3), and a polymerizable monomer having an active hydrogen in the molecule A monomer may be added during polymerization to produce the monomer.

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

  The kind of the polymerizable monomer that is additionally used is appropriately selected according to the characteristics required for the insulating layer. From the viewpoint of excellent durability against solvents and reducing the hysteresis of organic thin film transistors, monomers that have high molecular density and form a hard film are selected in films containing these compounds, such as styrene and styrene derivatives. . From the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode or the surface of the substrate, a polymer compound (A) to a polymer such as methacrylic acid ester and derivatives thereof, acrylic acid ester and derivatives thereof, and the like. A monomer that imparts plasticity to the compound (A-3) is selected.

  The acrylic acid esters and derivatives thereof may be monofunctional acrylates or polyfunctional acrylates although the amount of use is limited. Examples of acrylic acid esters and derivatives thereof include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-sec-butyl, and acrylic acid. Hexyl, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol di Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol Rupentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- ( Perfluoro-7-methyloctyl) ethyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9 -Hexadecafluorononyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N- An acryloyl morpholine is mentioned.

  The methacrylic acid esters and derivatives thereof may be monofunctional methacrylates, and may be polyfunctional methacrylates although the amount of use is limited. Examples of methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, -Sec-butyl acrylate, hexyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, Ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethyl Propane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (Perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3- Methylbutyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 1H, 1H, 3H-tetrafluoropropylme Acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H-1- (trifluoromethyl) trifluoro Examples thereof include ethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-acryloylmorpholine.

  Examples of styrene and derivatives thereof include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and 2,5-dimethylstyrene. 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m -Ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl Enyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2 , 4-Dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene , Divinylbenzene, divinylbiphenyl, diisopropylbenzene, o-trifluoromethylstyrene, m-trifluoromethylstyrene, p-trifluoromethylstyrene, o-2,2,2-trifluoroethylstyrene, m-2,2, 2-trifluoroethylstyrene, p-2,2,2-trif Oroethylstyrene, o-2,2,3,3,3-pentafluoropropylstyrene, m-2,2,3,3,3-pentafluoropropylstyrene, p-2,2,3,3,3- Examples include pentafluoropropylstyrene and pentafluorostyrene.

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

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

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

  Examples of the dialkyl ester of maleic acid and its derivatives include, for example, dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2 maleate -Ethylhexyl and dibenzyl maleate.

  Dialkyl esters of itaconic acid and derivatives thereof include, for example, dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2 itaconate -Ethylhexyl and dibenzyl itaconate are mentioned.

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

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

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

  As the polymerizable monomer used additionally, acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, acrylonitrile, methacrylonitrile and allyltrimethylgermanium are preferable.

  When the polymer compound (A) is produced using a monomer having an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent and an unsaturated bond in the molecule, the charged molar amount of the monomer Is preferably 5 mol% or more and 50 mol% or less, and more preferably 5 mol% or more and 40 mol% or less in all monomers involved in the polymerization. By adjusting the charged molar amount of the monomer within this range, a sufficient cross-linked structure is formed inside the insulating layer, the polar group content is kept at a low level, and polarization of the insulating layer is suppressed.

  The polystyrene equivalent weight average molecular weight of the polymer compound (A), the polymer compound (A-1), the polymer compound (A-2) and the polymer compound (A-3) is preferably 3,000 to 1,000,000. 500,000 is more preferable. The polymer compound (A), the polymer compound (A-1), the polymer compound (A-2) and the polymer compound (A-3) may be linear or branched, or may be cyclic. .

  Examples of the polymer compound (A) include poly (styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ] -Ethyl-methacrylate]), poly (styrene-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (styrene-co-acrylonitrile) -Co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyl trimer Tilgermanium), poly (styrene-co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), and poly ( Styrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]).

  Examples of the polymer compound (A-1) include poly (4- [1-ethoxyethoxy] styrene-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl. -Methacrylate]), poly (4- [1-ethoxyethoxy] styrene-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (4- [1-ethoxyethoxy] styrene-co-styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (4- [ 1-ethoxyethoxy] styrene-co-styrene-co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] Ethyl-methacrylate]), poly (4- [1-ethoxyethoxy] styrene-co-styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -Co-allyltrimethylgermanium), poly (4- [1-ethoxyethoxy] styrene-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ] -Ethyl-methacrylate]) and poly (4- [1-ethoxyethoxy] styrene-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxy] Amino] ethyl-methacrylate] -co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl- Methacrylate]).

  Examples of the polymer compound (A-2) include poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino]). Ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]) , Poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ( N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5 ' -Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino ) Carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium) and poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-4-methoxystyrene-co- [ 2- [O- (1′-methylpropylideneamino) carboxyamino ] Ethyl-methacrylate]).

  Examples of the polymer compound (A-3) include poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [O- (1 ′ -Methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [1'- (3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co -[2- [O- (1'-methylpropylideneamino) carboxya No] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co- [2- [1 '-(3' , 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co- [2 -[O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate- Co-styrene-co-acryloni Ril-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co 2-methacryloyloxyethyl methacrylate-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N -Diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl- Methacrylate] -co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonyl Amino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co- [2- [O -(1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate]- Co-styrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-Vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylo Tolyl-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinyl Phenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N -Diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino ) Carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, -Diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5'- Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co -Styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]) and poly (N, N-diethyldithiocarbamylmethylstyrene) -Co- [2- (4-vinylphenylaminocarbonylamino) ethyl ester Chrylate] -co-styrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- [2- [1 ′-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]).

<Active hydrogen compound (B)>
The organic thin film transistor insulating layer material of the present invention is an active hydrogen compound (B) containing a divalent organic group having a structure in which a disubstituted carbylene group is bonded to an oxycarbonyloxylene group and two or more active hydrogens in the molecule. including.

  In addition, a structure in which a disubstituted carbylene group is bonded to an oxycarbonyloxylene group is decomposed when an acid is acted on. Therefore, when used together with a photoacid generator, the organic thin film transistor insulating layer material of the present invention can exhibit a positive photosensitive function.

  As the active hydrogen compound (B), an active hydrogen compound represented by the formula (1) is preferable.

In formula (1), R ₁ and R ₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁ and R ₂ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ described above. Same as example. In one certain form, R < ₁ > and R < ₂ > is a methyl group.

  The active hydrogen compound (B) is preferably an active hydrogen compound represented by the formula (8).

In formula (8), R _{14 to} R ₂₁ and R _{26 to} R ₃₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _{14 to} R ₂₁ and R _{26 to} R ₃₃ are monovalent organic groups having 1 to 20 carbon atoms represented by R ′ described above. The definition and specific examples of the organic group are the same. In one certain form, R < ₁₄ > -R < ₂₁ > and R < ₂₆ > -R < ₃₃ > are hydrogen atoms.

In formula (8), R _{22 to} R ₂₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _{22 to} R ₂₅ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by the aforementioned R ′. Same as example. In one certain form, R < ₂₂ > -R < ₂₅ > is a methyl group.

R _aaa , R _bbb and R _ccc each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.

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

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

  Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms that may be substituted with an alkyl group or the like include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.

In formula (8), X ₁ and X ₂ each independently represent an amino group, a substituted amino group, a hydroxyl group or a thiol group. Here, the substituted amino group is a group in which a hydrogen atom in the amino group is substituted with a substituent, and examples thereof include an amino group substituted with an alkyl group and an amino group substituted with an aromatic hydrocarbon group. Examples of the amino group substituted with an alkyl group include a methylamino group, an ethylamino group, a propylamino group, and a butylamino group. Examples of the amino group substituted with an aromatic hydrocarbon group include a phenylamino group. In one certain form, X < ₁ > and X < ₂ > are amino groups.

  In formula (8), p1, p2 and p3 each independently represent an integer of 0 or 1. In one certain form, p1 and p3 are 0, and p2 is 1.

  The active hydrogen compound (B) is prepared, for example, by reacting bromophenyl chloroformate with 2,5-dimethylhexane-2,5-diol in the presence of a deoxidizer to produce a reaction intermediate. The product can be produced by a method of coupling the aminophenylboronic acid pinacol ester.

  Examples of the active hydrogen compound (B) include 2,3-bis (4′-aminobiphenyl-4-oxycarbonyloxy) butane and 2,5-bis (4′-aminobiphenyl-4-oxycarbonyloxy) hexane. Is mentioned.

  When the organic thin film transistor insulating layer material of the present invention contains a polymer compound (A-2), the organic thin film transistor insulating layer material has an unsaturated double bond compound having two or more unsaturated double bonds in the molecule. (C) may be contained.

  The terminal unsaturated double bond contained in the unsaturated double bond compound (C) reacts and polymerizes with the benzyl radical provided by the polymer compound (A-2). Since the polymerization reaction proceeds in a living manner, a cured film having a high crosslinking density is formed. At that time, the radical reaction proceeds in parallel with the reaction between the second functional group and active hydrogen, and the crosslink density of the organic thin film transistor insulating layer material is effectively increased.

  As said unsaturated double bond compound (C), the unsaturated double bond compound represented by Formula (9) is preferable.

In formula (9), R _{34 to} R ₃₈ and R _{43 to} R ₄₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _{34 to} R ₃₈ and R _{43 to} R ₄₇ are the monovalent monovalent organic groups having 1 to 20 carbon atoms represented by R ′ described above. The definition and specific examples of the organic group are the same. In one certain form, R < ₃₄ > -R < ₃₈ > and R < ₄₃ > -R < ₄₇ > are hydrogen atoms.

In formula (9), R _{39 to} R ₄₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _{39 to} R ₄₂ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ described above. Same as example. In one certain form, R < ₃₉ > -R < ₄₂ > is a methyl group.

R _ddd , R _eeee and R _fff each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the divalent organic group having 1 to 20 carbon atoms represented by R _ddd , R _eeee and R _fff are those having 1 to 20 carbon atoms represented by the aforementioned R _aaa , R _bbb and R _ccc The definition and specific examples of the divalent organic group are the same.

  In formula (9), p4, p5 and p6 each independently represent an integer of 0 or 1. In one embodiment, p4 is 1, p5 is 1, and p6 is 1.

  The unsaturated double bond compound (C) can be produced, for example, by the same method as the active hydrogen compound (B). Specifically, a reaction intermediate is produced by reacting bromophenyl chloroformate with 2,5-dimethylhexane-2,5-diol in the presence of a deoxidizer, and the reaction intermediate and vinylphenylboron are produced. It can be produced by a method of coupling with an acid.

  Examples of the unsaturated double bond compound (C) include 2,3-bis (4′-vinylbiphenyl-4-oxycarbonyloxy) butane and 2,5-bis (4′-vinylbiphenyl-4-oxycarbonyl). Oxy) hexane.

  The addition amount of the active hydrogen compound (B) contained in the organic thin film transistor insulating layer material of the present invention is 0.1 to the amount of the repeating unit having the first functional group in the polymer compound (A). 10 equivalent is preferable and 0.3-5 equivalent is more preferable. When the amount of the active hydrogen compound (B) added is outside the above range, the formation of the crosslinked structure may be insufficient.

The organic thin film transistor insulating layer material of the present invention contains a solvent for mixing and viscosity adjustment, a crosslinking agent used for crosslinking the polymer compound (A), an additive used in combination with the crosslinking agent, and the like. It's okay. Solvents used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic carbonization such as xylene. Examples thereof include a hydrogen solvent, a ketone solvent such as acetone, an acetate solvent such as butyl acetate, an alcohol solvent such as isopropyl alcohol, a halogen solvent such as chloroform, and a mixed solvent of these solvents. Moreover, as an additive, the catalyst for promoting a crosslinking reaction, a sensitizer, a leveling agent, a viscosity modifier, etc. can be used.
Examples of the catalyst for promoting the crosslinking reaction include a photoacid generator, a thermal acid generator, and a photocationic polymerization initiator.

It is preferable to add a photoacid generator or a thermal acid generator to the organic thin film transistor insulating layer material of the present invention. Examples of the photoacid generator and thermal acid generator include diazomethane derivatives, triazine derivatives, iodonium salts, and sulfonium salts. Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane. Examples of the triazine derivative include 2-methyl-4,6-ditrichloromethyl-triazine. Examples of the iodonium salt include tolylcumyl iodonium tetrakis (pentafluorophenyl) borate. Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate.
As the photoacid generator and thermal acid generator, in addition to the above materials, compounds described in JP-A-9-118663 and compounds described in JP-A-2007-262401 can also be used.

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

  The organic thin film transistor insulating layer material of the present invention does not need to contain fluorine. Therefore, according to the present invention, it is possible to provide an organic thin film transistor insulating layer that has a low absolute value of threshold voltage and low hysteresis and does not contain fluorine as necessary. The surface of the organic thin film transistor insulating layer containing no fluorine is excellent in affinity with an organic material. As a result, for example, when the organic semiconductor layer is formed adjacent to the organic thin film transistor insulating layer, the adhesion between the two becomes good. In that case, the flatness of the surface of the formed organic semiconductor layer is improved.

  In addition, since the organic thin film transistor insulating layer material does not contain fluorine atoms, an insulating layer coating solution containing the organic thin film transistor insulating layer material and a solution containing no fluorine is applied to a bank having a lyophilic portion and a liquid repellent portion. When the organic thin film transistor insulating layer is formed, the movement of the insulating layer coating liquid to the liquid repellent portion of the bank can be suppressed.

  When forming an organic semiconductor layer by applying an organic semiconductor coating liquid containing an organic semiconductor compound and a fluorine-free solvent on the organic thin film transistor insulating layer, the film and the organic thin film transistor insulating layer have excellent affinity. A uniform organic semiconductor layer can be formed.

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

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

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

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

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

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

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

  When the first functional group contained in the polymer compound (A) is a functional group that generates a second functional group that reacts with active hydrogen upon irradiation with electromagnetic waves or electron beams, the organic thin-film transistor insulating layer is organic It may be formed by a forming method including a step of applying a liquid containing a thin film transistor insulating layer material to a substrate to form a coating layer on the substrate, and a step of irradiating the coating layer with an electromagnetic wave or an electron beam. preferable.

  When the first functional group contained in the polymer compound (A) is a functional group that generates a second functional group that reacts with active hydrogen by the action of heat, a liquid containing an organic thin film transistor insulating layer material is used. Preferably, the organic thin film transistor insulating layer is formed of an organic thin film transistor insulating layer, which includes a step of applying to a material to form a coating layer on the substrate and a step of irradiating the coating layer with electromagnetic waves or electron beams. A step of applying a liquid containing a thin film transistor insulating layer material to a substrate to form a coating layer on the substrate, a step of irradiating the coating layer with electromagnetic waves or an electron beam, and a step of applying heat to the coating layer It is more preferable to form by the formation method including this.

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

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

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

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

  Irradiation with ultraviolet rays can be performed using, for example, an exposure apparatus used for manufacturing a semiconductor or a UV lamp used for curing a UV curable resin. The electron beam irradiation can be performed using, for example, a micro electron beam irradiation tube. Heating can be performed using a heater, an oven, or the like.

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

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

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

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

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

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

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

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention, it cannot be overemphasized that this invention is not limited by an Example.

<Synthesis Example 1>
(Synthesis of polymer compound 1)
In a 50 ml pressure vessel (Ace), 2.50 g of 4- (1-ethoxyethoxy) styrene (Tosoh Organic Synthesis), 4.80 g of 4-vinylanisole (Aldrich), 2- (O- [1 ′ -Methylpropylideneamino] carboxyamino] ethyl-methacrylate (produced by Showa Denko, trade name “Karenz MOI-BM”) 3.13 g, 2- [N- [1 ′, 3′-dimethylpyrazolyl] carbonylamino) ethyl -0.82 g of methacrylate (made by Showa Denko, trade name “Karenz MOI-BP”), 0.06 g of 2,2′-azobis (2-methylpropionitrile), and 26 of 2-heptanone (manufactured by Tokyo Chemical Industry) .37 g was added, and argon gas was bubbled and sealed. Polymerization was performed in an oil bath at 60 ° C. for 20 hours to obtain a viscous 2-heptanone solution in which the polymer compound 1 was dissolved. The high molecular compound 1 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

高分子化合物１

Polymer compound 1

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 1 was 76000 (Shimadzu GPC, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

<Synthesis Example 2>
(Synthesis of polymer compound 2)
1.88 g of 2,1,3-benzothiadiazole-4,7-di (ethylene boronate) and 2,6-dibromo- (4,4-bis-hexadecanyl-4H-cyclopenta [2,1-b; In toluene (80 mL) containing 3.81 g of 3,4-b ′]-dithiophene), under nitrogen, 0.75 g of tetrakis (triphenylphosphine) palladium, methyltrioctylammonium chloride (manufactured by Aldrich, trade name “ 1.0 g of Aliquat 336 "(registered trademark)) and 24 mL of 2M aqueous sodium carbonate solution were added. The mixture was stirred vigorously and heated to reflux for 24 hours. The viscous reaction mixture was poured into 500 mL of acetone to precipitate a fibrous yellow polymer. The polymer was collected by filtration, washed with acetone and dried in a vacuum oven at 60 ° C. overnight. The resulting polymer is referred to as polymer compound 2. The high molecular compound 2 has the following repeating unit. n indicates the number of repeating units.

高分子化合物２

Polymer compound 2

<Synthesis Example 3>
(Synthesis of active hydrogen compound 1)
In a 150 ml three-necked flask equipped with a septum and a three-way cock, 5.00 g of 4-bromo-phenylchloroformate, 4.29 g of triethylamine, and 100 ml of dehydrated tetrahydrofuran were placed and cooled in an ice bath. 1.55-g of 2,5-dimethyl-2,5-hexanediol was slowly added dropwise from a gas tight syringe. After completion of the dropwise addition, the mixture was reacted by stirring for 1 hour in an ice bath, and further stirred overnight at room temperature. After completion of the reaction, the reaction mixture was poured into water, the product was extracted with diethyl ether, the organic layer was further washed with water, then separated, and the organic layer was dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was filtered off, the filtrate was concentrated by a rotary evaporator to obtain 2,5-bis (4-bromophenyloxycarbonyloxy) -2.5-dimethylhexane as a viscous liquid. The yield of 2,5-bis (4-bromophenyloxycarbonyloxy) -2.5-dimethylhexane was 5.12 g.

２，５−ビス（４−ブロモフェニルオキシカルボニルオキシ）−２．５−ジメチルヘキサン

2,5-bis (4-bromophenyloxycarbonyloxy) -2.5-dimethylhexane

  To a 300 ml three-necked flask equipped with a Dimroth with a three-way cock, 5.08 g of the obtained 2,5-bis (4-bromophenyloxycarbonyloxy) -2.5-dimethylhexane, 4- (4 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (Tokyo Chemical Industry Co., Ltd.) 4.22 g, potassium carbonate (Wako Pure Chemical Industries) 6.45 g, toluene (Wako Pure) The product was bubbled with argon to make the inside of the flask an argon atmosphere while stirring with a magnetic stirrer. 0.076 g of [1,1′-bis (diphenylphosphinoferrocene)] dichloropalladium (II) dichloromethane complex (manufactured by Aldrich) was added to the flask, and the flask was immersed in an oil bath at 80 ° C. while continuing argon bubbling. The reaction was performed for 6 hours. After completion of the reaction, the reaction solution was returned to room temperature, and the reaction mixture was transferred to a 500 ml separatory funnel. The flask was washed with 100 ml of toluene, and the washing solution was transferred to a separatory funnel. After the aqueous layer was separated, 50 ml of ion-exchanged water was added to the organic layer, the organic layer was washed with water, and the aqueous layer was separated. The water washing process was repeated 3 times. After completion of washing with water, the organic layer was separated and dried over anhydrous magnesium sulfate. After completion of drying, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator. 100 ml of hexane is added to the resulting viscous liquid to precipitate a solid, and the solid is filtered off with a glass filter and dried under reduced pressure to give 2,5-bis (4 ′-(4-aminobiphenyl) oxycarbonyl. Oxy) -2,5-dimethylhexane (active hydrogen compound 1) was obtained as pale yellow needles. The yield of active hydrogen compound 1 was 4.59 g.

活性水素化合物１

Active hydrogen compound 1

<Example 1>
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
In a 10 ml sample bottle, 8.00 g of the 2-heptanone solution of the polymer compound 1 obtained in Synthesis Example 1, 0.215 g of the active hydrogen compound 1 obtained in Synthesis Example 3, and a photoacid generator (MBZ-101; 0.24 g (Midori Kagaku) was added and dissolved while stirring to prepare a uniform coating solution 1 as an organic thin film transistor insulating layer material.

The obtained coating solution 1 was filtered using a membrane filter having a pore size of 0.2 μm, spin-coated on a glass substrate with a chromium electrode, and baked on a hot plate at 100 ° C. for 60 minutes. Thereafter, UV light (wavelength 365 nm) was irradiated at 1800 mJ / cm ² using an aligner (manufactured by Canon; PLA-521) and baked in nitrogen at 220 ° C. for 30 minutes to obtain a gate insulating layer. The film thickness of the gate insulating layer was 576 nm.

  Next, the polymer compound 2 was dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and the solution was filtered through a membrane filter to prepare a coating solution. .

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

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

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

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

  A field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the coating solution 2 was used in place of the coating solution 1 and UV irradiation was not performed when the gate insulating layer was formed, and the transistor characteristics were measured. The results are shown in Table 1.

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

Claims (14)

In the molecule, a polymer compound (A) containing a repeating unit containing the following first functional group,

(1)
[Wherein, R ₁ and R ₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ]
An organic thin film transistor insulating layer material comprising an active hydrogen compound (B) containing a divalent organic group represented by formula (2) and two or more active hydrogens;
First functional group: a functional group capable of generating a second functional group capable of reacting with active hydrogen by the irradiation of electromagnetic waves or the action of heat. The polymer compound (A) further has the formula

(2)
[Wherein R ₃ represents a hydrogen atom or a methyl group. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. R represents an organic group that can be removed by an acid. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. a represents an integer of 0 or 1, and n1 represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of R ′, they may be the same or different. ]
The organic thin film transistor insulating layer material according to claim 1, which is a polymer compound (A-1) containing a repeating unit represented by: The polymer compound (A) further has the formula

(3)
[Wherein, R ₄ represents a hydrogen atom or a methyl group. R ₅ and R ₆ represent a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _bb represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. b represents an integer of 0 or 1, and n2 represents an integer of 1 to 5. When there are a plurality of R ₅ , they may be the same or different. When there are a plurality of R _{6 s} , they may be the same or different. When there are a plurality of R ″, they may be the same or different. ]
The organic thin film transistor insulating layer material according to claim 1, which is a polymer compound (A-2) containing a repeating unit represented by the formula: The polymer compound (A-2) is further represented by the formula:

(4)
[Wherein, R ₇ represents a hydrogen atom or a methyl group. R _cc represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. c represents an integer of 0 or 1. ]
The repeating unit represented by

(5)
[Wherein R ₈ represents a hydrogen atom or a methyl group. R ′ ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _dd represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. d represents an integer of 0 or 1. m represents an integer of 1 to 5. When there are a plurality of R ′ ″, they may be the same or different. ]
The organic thin film transistor insulating layer material according to claim 3, which is a polymer compound (A-3) containing at least one repeating unit selected from the group consisting of repeating units represented by:   The first functional group is at least one group selected from the group consisting of an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent. The organic thin-film transistor insulating layer material described in 1. The isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula

(6)
[Wherein, Xa represents an oxygen atom or a sulfur atom, and R ₉ and R ₁₀ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The organic thin film transistor insulating layer material according to claim 5, which is a group represented by: Isocyanato groups blocked with blocking agents and isothiocyanato groups blocked with blocking agents are represented by the formula

(7)
[Wherein, Xb represents an oxygen atom or a sulfur atom, and R _{11 to} R ₁₃ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The organic thin film transistor insulating layer material according to claim 5, which is a group represented by: The active hydrogen compound (B) has the formula

(8)
[Wherein, R _{14 to} R ₂₁ and R _{26 to} R ₃₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _{22 to} R ₂₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _aaa , R _bbb and R _ccc each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. X ₁ and X ₂ each independently represent an amino group, a substituted amino group, a hydroxyl group or a thiol group. p1, p2 and p3 each independently represents an integer of 0 or 1. ]
The organic thin film transistor insulating layer material according to claim 1, wherein the organic thin film transistor insulating layer material is an active hydrogen compound represented by the formula:   Furthermore, the organic thin-film transistor insulating-layer material as described in any one of Claims 3-8 containing the unsaturated double bond compound (C) which has a 2 or more unsaturated double bond in a molecule | numerator. The unsaturated double bond compound (C) has the formula

(9)
[Wherein, R _{34 to} R ₃₈ and R _{43 to} R ₄₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _{39 to} R ₄₂ each independently represents a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _ddd, R _eee and _{R fff} each independently represent a divalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. p4, p5 and p6 each independently represent an integer of 0 or 1. ]
The organic thin film transistor insulating layer material according to claim 9, which is an unsaturated double bond compound represented by:   The organic thin-film transistor which has the organic thin-film transistor insulating layer formed using the organic thin-film transistor insulating-layer material as described in any one of Claims 1-10.   The organic thin film transistor according to claim 11, wherein the organic thin film transistor insulating layer is a gate insulating layer.   The member for a display containing the organic thin-film transistor of Claim 11 or 12.   A display comprising the display member according to claim 13.

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