JP2013125902A - Organic thin film transistor insulation layer material and organic thin film transistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film transistor insulation layer material which allows for simple formation of a through part such as a via hole in an organic thin film transistor insulation layer.SOLUTION: The organic thin film transistor insulation layer material contains, in a molecule, a polymer compound (A) including a repeating unit containing a following first functional group, and a repeating unit represented by a formula (in the formula, Rrepresents a hydrogen atom or a methyl group, Rrepresents a coupling part, R represents an organic group which can be detached by acid, R' represents a hydrogen atom or a monovalent organic group of 1-20C, (a) represents an integer of 0 or 1, and n represents an integer of 1-5), and a compound (B) capable of generating acid by irradiation with electromagnetic waves or an electron beam and having a thermal decomposition temperature of 200°C or lower.

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 type organic thin film transistor which is a kind of organic thin film transistor, a voltage applied to a gate electrode acts on an organic semiconductor layer through a gate insulating layer to control the amount of drain current. Further, the gate insulating layer formed between the gate electrode and the organic semiconductor layer prevents drain current from flowing to the gate electrode.

  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 element structure of a top gate type organic field effect transistor which is a kind of field effect type organic thin film transistor, 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 interface formed on the organic semiconductor layer side of the film formed from the organic thin film transistor gate insulating layer material 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.

  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.

JP2007-305950A

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

  However, in consideration of practical use such as driving a light emitting element such as an organic electroluminescence element (organic EL element), a through-hole such as a via hole is formed in the insulating layer formed between the upper electrode and the lower gate electrode. It is necessary to join the upper electrode and the lower gate electrode.

  However, the above-described conventional materials do not have photosensitivity and are difficult to pattern when forming an insulating layer. Therefore, in order to form a through-hole such as a via hole in such an insulating layer, first, a liquid containing a resist material is applied on the insulating layer, and a resist layer is formed, and the resist layer is exposed through a mask. A step of developing the resist layer to form a pattern of the resist layer, a step of transferring the pattern to the insulating layer using the resist layer on which the pattern is formed as a mask, and a step of peeling and removing the resist layer on which the pattern is formed There is a problem that it is necessary and the manufacturing process becomes complicated.

  An object of the present invention is to provide an organic thin film transistor insulating layer material capable of forming through portions that need to be formed at predetermined positions, such as via holes, in an insulating layer of an organic thin film transistor by a simple process. .

  That is, the present invention relates to a repeating unit containing the following first functional group in the molecule and a formula:

（１）

(1)

[Wherein, R ₁ 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 n represents an integer of 1 to 5. ]
A polymer compound (A) containing a repeating unit represented by:
A compound capable of generating an acid upon irradiation with an electromagnetic wave or an electron beam and having a thermal decomposition temperature of 200 ° C. or lower, (B)
An organic thin film transistor insulating layer material is provided.
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.

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

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

（３）

(3)

[Wherein, Xa represents an oxygen atom or a sulfur atom, and R ₆ and R ₇ 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 of the formula

（４）

(4)

[Wherein, Xb represents an oxygen atom or a sulfur atom, and R ₈ , 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 certain form, the said high molecular compound (A) is further Formula.

（２）

(2)

[Wherein R ₂ represents a hydrogen atom or a methyl group. 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 an organic group that can be eliminated 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. b represents an integer of 0 or 1, and m represents an integer of 1 to 5. ]
It is a high molecular compound (A-1) which has a repeating unit represented by these.

The present invention also includes a step of applying a liquid containing the organic thin film transistor insulating layer material to a substrate to form a coating layer on the substrate;
Irradiating a part of the coating layer with an electromagnetic wave or an electron beam through a mask;
Developing a portion of the coating layer irradiated with electromagnetic waves or electron beams to form a pattern on the coating layer; and
Applying heat to the coating layer on which the pattern is formed;
The manufacturing method of the organic thin-film transistor insulating layer containing this is provided.

  In one certain form, the said electromagnetic wave is an ultraviolet-ray.

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

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

  In addition, the present invention provides a display member including the organic thin film transistor.

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

  The organic thin film transistor insulating layer material of the present invention can easily form an insulating layer having a via hole, and further provides an organic thin film transistor insulating layer having excellent characteristics. In the organic thin film transistor using the organic thin film transistor insulating layer material of the present invention, for example, the leakage current is reduced.

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.

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

<Polymer Compound (A)>
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. On the other hand, the “low molecular compound” means a compound that does not have the same structural unit repeatedly in the molecule.

  The organic thin film transistor insulating layer material of the present invention contains a polymer compound (A), and the polymer compound (A) is represented by the repeating unit containing the first functional group in the molecule and the formula (1). Containing repeating units. The first functional group is a functional group that can generate a second functional group capable of reacting with active hydrogen by irradiation with electromagnetic waves or the action of heat.

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

In formula (1), 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 represented by R _aa may be linear, branched or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Also good. 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. And a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with a group, a divalent cyclic hydrocarbon group having 3 to 20 carbon atoms and an alkyl group. Among them, a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, 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.

  Examples of the divalent linear aliphatic hydrocarbon group, the divalent branched aliphatic hydrocarbon group, and the divalent cyclic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Hexylene group, isopropylene group, isobutylene group, 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 ethylanthrone And a rylene group.

  In formula (1), the side chain portion is a phenyl group having a substituent. The presence of the phenyl moiety in the organic thin film transistor insulating layer material improves the crystallinity of the formed organic thin film transistor insulating layer, and as a result, the performance as the organic thin film transistor insulating layer is improved.

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

  Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and 3 carbon atoms. -20 cyclic hydrocarbon group and C6-C20 aromatic hydrocarbon group are mentioned, Preferably, C1-C6 linear hydrocarbon group, C3-C6 branched hydrocarbon group , A cyclic hydrocarbon group having 3 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

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

  In formula (1), R represents an organic group that can be eliminated by an acid. This means that in the formula (1), when an acid acts on the —COOR group, the R group is eliminated and a —COOH group is generated. In that case, the polymer compound (A) shows acidity, and as a result, becomes soluble in an alkaline solution.

  Examples of the organic group that can be eliminated by an acid include a hydrocarbon group having 4 to 20 carbon atoms having a branched structure or a cyclic hydrocarbon structure, an optionally substituted hydrocarbonyl group, and an optionally substituted hydropyranyl group. Can be mentioned.

  Examples of the hydrocarbon group having 4 to 20 carbon atoms having a branched structure include a tertiary butyl group, a 2,3-dimethyl-2-butyl group, and a 2,3,3-trimethyl-2-butyl group.

  Examples of the hydrocarbon group having 4 to 20 carbon atoms having a cyclic hydrocarbon structure include 2-cyclopropyl-2-propyl group, 1-methyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1- Examples thereof include a methyl-1-cycloheptanyl group, a 2-methyl-2-adamantyl group, and a 2-adamantyl-2-propyl group.

  Examples of the substituent that the hydrofuranyl group and the hydropyranyl group may have include a hydroxy group, an alkoxy group, and an alkyl group.

  The hydrofuranyl group means a group obtained by removing one hydrogen atom from dihydrofuran or tetrahydrofuran, and examples of the optionally substituted hydrofuranyl group include a tetrahydrofuranyl group.

  The hydropyranyl group means a group obtained by removing one hydrogen atom from dihydropyran or tetrahydropyran. Examples of the hydropyranyl group which may be substituted include a tetrahydropyranyl group and a 4-methoxytetrahydropyranyl group. It is done.

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

  The first functional group contained in the molecule of the polymer compound (A) does not react with active hydrogen. However, when the first functional group is irradiated with electromagnetic waves or heat is applied, the second functional group is And the second functional group reacts with active hydrogen. That is, the first functional group is deprotected by the irradiation of electromagnetic waves or the action of heat to generate a second functional group that reacts with active hydrogen. The second functional group reacts with and binds to the active hydrogen-containing group contained in the molecule of the polymer compound (A), thereby forming a crosslinked structure inside the insulating layer.

  Here, the 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.

  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 active hydrogen-containing group contained in the molecule of the polymer compound (A) is, for example, from the -COOR group to R in the formula (1) by the action of an acid generated from the compound (B) capable of generating an acid. Examples thereof include a carboxyl group generated by elimination of a group. Further, for example, a hydroxyl group generated by elimination of an R group from an —OR group in formula (2) by the action of an acid generated from a compound (B) capable of generating an acid can be mentioned.

  The second functional group is protected (blocked) until irradiation with electromagnetic waves or heat is applied in the step of forming the organic thin film transistor insulating layer, and the organic thin film transistor insulating layer is in the form of the first functional group. Present in the material. 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 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. A blocking agent may be used individually and may be used in mixture of 2 or more types. 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 compound include formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, 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.

  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 are represented by the group represented by the formula (3) and the formula (4). Are preferred.

In Formula (3) and Formula (4), Xa represents an oxygen atom or a sulfur atom, Xb represents an oxygen atom or a sulfur atom, and R _{6 to} R ₁₀ 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 represented by R _{6 to} R ₁₀ 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 represented by R _{6 to} R ₁₀ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, 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 Nsuriru groups include chlorophenyl group and a bromophenyl group.

The monovalent organic group having 1 to 20 carbon atoms represented by R _{6 to} R ₁₀ is preferably an alkyl group.

In one certain form, R < ₆ > -R < ₁₀ > 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.

  The polymer compound (A) used in the present invention is preferably a polymer compound (A-1) having a repeating unit represented by the formula (2).

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

In formula (2), R _bb represents a linking moiety that connects 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. b represents an integer of 0 or 1. In one certain form, b is 0.

Specific examples of the divalent organic group having 1 to 20 carbon atoms represented by R _bb are the same as the specific examples of the divalent organic group having 1 to 20 carbon atoms represented by R _aa described above.

  In formula (2), R ″ represents an organic group that can be eliminated by an acid. This means that, in the formula (2), when an acid acts on the —OR ″ group, the R ″ group is eliminated and an —OH group is generated. In that case, the generated —OH group can react with the carboxyl group or the second functional group contained in the organic thin film transistor insulating layer material to form a crosslinked structure inside the organic thin film transistor insulating layer. .

  In addition, the carboxyl group contained in the organic thin film transistor insulating layer material is, for example, the R group is eliminated from the —COOR group in the formula (1) by the action of the acid generated from the compound (B) capable of generating an acid. Generated. The second functional group contained in the organic thin film transistor insulating layer material is generated by deprotection of the first functional group by the action of electromagnetic waves or heat, for example.

  Examples of the organic group that can be eliminated by an acid include an optionally substituted alkoxyalkyl group having 2 to 20 carbon atoms, an optionally substituted hydrocarbonyl group, an optionally substituted hydropyranyl group, and 3 carbon atoms. Groups having a cyclic hydrocarbon structure of ˜20.

  Examples of the substituent that the alkoxyalkyl group having 2 to 20 carbon atoms may have include an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a halogen atom, and a phenyl group. . Examples of the optionally substituted alkoxyalkyl group having 2 to 20 carbon atoms include a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a 2-ethoxyethyl group, and bis (2-chloroethoxy) methyl. Group, 1-methyl-1-methoxyethyl group, 1-isopropoxyethyl group.

  Examples of the substituent that the hydrofuranyl group and the hydropyranyl group may have include a hydroxy group, an alkoxy group, and an alkyl group.

  The hydrofuranyl group means a group obtained by removing one hydrogen atom from dihydrofuran or tetrahydrofuran, and examples of the optionally substituted hydrofuranyl group include a tetrahydrofuranyl group.

  The hydropyranyl group means a group obtained by removing one hydrogen atom from dihydropyran or tetrahydropyran. Examples of the hydropyranyl group which may be substituted include a tetrahydropyranyl group and a 4-methoxytetrahydropyranyl group. It is done.

  Examples of the group having a cyclic hydrocarbon structure having 3 to 20 carbon atoms include 1-cyclopropyl-1-methylethyl group, 1-methyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, and 1-methyl. Examples include a -1-cycloheptanyl group, a 2-methyl-2-adamantyl group, and a 1-methyl-1- (2-adamantyl) ethyl group.

  In formula (2), m represents an integer of 1 to 5. In one certain form, m is 1.

  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 having 1 to 20 carbon atoms may be substituted with a fluorine atom.

  Specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ ″ are the same as the specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ described above. .

  The polymer compound (A) is obtained by, for example, converting a polymerizable monomer mixture containing a polymerizable monomer containing the first functional group and a polymerizable monomer serving as a raw material of the repeating unit represented by the formula (1), It can be produced by a method of copolymerization using a polymerization initiator or a thermal polymerization initiator.

  Examples of the polymerizable monomer containing the first functional group include monomers having in the molecule either an isocyanato group blocked with a blocking agent, an isothiocyanate group blocked with a blocking agent, and an unsaturated bond. Can be mentioned. The monomer having an isocyanato group blocked with the blocking agent and an isothiocyanato group blocked with the blocking agent and an unsaturated bond in the molecule has an isocyanato group or an isothiocyanato group and an unsaturated bond in the molecule. It can be produced by reacting a compound 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.

  The blocking agent can be suitably used for the production of the polymerizable monomer containing the first functional group. Isocyanato group or isothiocyanato group blocked with a blocking agent by reacting an isocyanato group or a compound having an isothiocyanato group and an unsaturated bond in the molecule with a blocking agent, and an isothiocyanato group blocked with a blocking agent or an unsaturated bond In the reaction for producing a monomer having in the molecule, an organic solvent, a catalyst and 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 copolymerization, the wavelength of light irradiated to the polymerizable monomer is 360 nm or more, preferably 360 to 450 nm.

  The thermal polymerization initiator may be any compound that serves as a radical polymerization initiator. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylpropane) ), Azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyl peroxide Oxide, benzoyl peroxide, 2,4-dichlorobenzoyl 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.

  Examples of the monomer that is a raw material of the repeating unit represented by the formula (1) include tertiary butyl-4-vinylbenzoate, (2-methyl-2-adamantyl) -4-vinylbenzoate, and (tetrahydro-2 -Pyranyl] -4-vinylbenzoate.

  The polymer compound (A-1) includes, 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 (1), and the formula (2). It can be produced by a method similar to the production of the polymer compound (A) using a polymerizable monomer mixture containing a polymerizable monomer as a raw material for the repeating unit.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (2) include 4- (methoxymethoxy) styrene, 4- (methoxyethoxymethoxy) styrene, 4- (1-ethoxyethoxy) styrene, 4 Examples include-(2-tetrahydropyranyloxy) styrene, 4- (cyclopropylmethoxy) styrene, and 4- (cyclohexyloxy) styrene.

  The polymer compound (A) is produced by adding a polymerizable monomer other than the polymerizable monomer containing the first functional group and the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (1) during the polymerization. May be.

  The polymer compound (A-1) is represented by a polymerizable monomer containing a first functional group, a polymerizable monomer that is a raw material for the repeating unit represented by the formula (1), and the formula (2). It may be produced by adding a polymerizable monomer other than the polymerizable monomer that is a raw material of the repeating unit during the polymerization.

  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, organogermanium derivatives containing unsaturated hydrocarbon groups, vinyl-1,3-dioxolan-2-one and derivatives thereof.

  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, the polymer compound (A) or 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-1) is selected.

  The acrylate ester and its derivative may be a monofunctional acrylate or a polyfunctional acrylate 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, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic Acid-3-hydroxypropyl, 2-hydroxybutyl acrylate, 2-hydroxyphenylethyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol di Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3- Pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2 -(Perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acetate Relate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluorocarbon) Fluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro -7-methyloctyl) -2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1 H, 9H-hexadecafluorononyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-acryloylmorpholine.

  The methacrylic acid ester 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, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacryl Acid-sec-butyl, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, meta 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, ethylene glycol Coal dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol penta Methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 3-perfluorobutyl-2- Hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- Perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl methacrylate, 3- (per Fluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- ( Perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate Relate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-acryloyl morpho Phosphorus is mentioned.

  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, o-hydroxystyrene, m-hydroxystyrene, p-hydride Xylstyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl Toluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl -Α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene and 4-aminostyrene.

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

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

  Examples of vinyl-1,3-dioxolan-2-one and derivatives thereof include 4-vinyl-1,3-dioxolan-2-one and 5-methyl-4-vinyl-1,3-dioxolane-2- ON.

  Additional polymerizable monomers used include acrylic acid alkyl esters, methacrylic acid alkyl esters, styrene, 4-methoxystyrene, acrylonitrile, methacrylonitrile, allyltrimethylgermanium, and 4-vinyl-1,3-dioxolane- 2-one is preferred.

  The charged molar amount of the polymerizable monomer containing the first functional group in the polymer compound (A) and the polymer compound (A-1) is preferably 5 mol% in all the polymerizable monomers involved in the polymerization. It is 50 mol% or less, More preferably, it is 5 mol% or more and 40 mol% or less. By adjusting the charged molar amount of the polymerizable monomer containing the first functional group within this range, a sufficient cross-linking structure is formed inside the insulating layer, and the content of the polar group is kept at a low level. Is suppressed.

  The charged molar amount of the polymerizable monomer that is the raw material of the repeating unit represented by the formula (1) in the polymer compound (A) and the polymer compound (A-1) is the same among all the polymerizable monomers involved in the polymerization. Preferably, it is 20 mol% or more and 70 mol% or less, More preferably, it is 30 mol% or more and 60 mol% or less. If the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is less than 20 mol%, the solubility in an alkali developer may be insufficient and development may not be possible. When the charged molar amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (1) exceeds 70 mol%, the dissolution contrast may be lowered and the resolution may be deteriorated.

  3000-1 million are preferable and, as for the weight average molecular weight of polystyrene conversion of a high molecular compound (A) and a high molecular compound (A-1), 5000-500000 are more preferable. The polymer compound (A) and the polymer compound (A-1) may be linear, branched or cyclic.

  Examples of the polymer compound (A) include poly (tertiary-butyl-4-vinylbenzoate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) ) -4-vinylbenzoate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-acrylonitrile-co -[2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ( 2-tetrahydropyranyl) -4-vinylbenzoate-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2 -Adamantyl) -4-vinylbenzoate-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate) -Co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co -4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxya No] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxy] Amino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), Poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2- Methyl-2-adamantyl) -4-vinylbenzoate-co-styrene-co- [2- [O- (1′-methylpropylideneamino Carboxyamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-2,3,4,5,6-pentafluorostyrene-co- [2- [O- (1'-methyl Propylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4-2,3,4,5,6-pentafluorostyrene-co- [2 -[O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((1-methyladamantyl) -4-vinylbenzoate-co-4-2,3,4,5,6- Pentafluorostyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (tertiary -Butyl-4-vinylbenzoate-co-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino ] Ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [ 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4-2,3,4, 5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]) Poly (tertiary-butyl-4-vinylbenzoate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl)- 4-vinylbenzoate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-acrylonitrile-co- [2- [1 ′ -(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl)- 4-vinylbenzoate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4 -Vinylbenzoate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co- 4-methoxystyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co- 4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacryl Rate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] Ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), Poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (( 2-Methyl-2-adamantyl) -4-vinylbenzoate-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonyl Mino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-2,3,4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5 '-Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4-2,3,4,5,6-pentafluorostyrene-co- [ 2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4-2,3 4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (tertiary Butyl-4-vinylbenzoate-co-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonyl Amino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), and poly ((1-methyladamantyl) -4-vinylbenzoate-co-4-2,3,4 , 5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] ).

  Examples of the polymer compound (A-1) include poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [O- (1′-methyl). Propylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [O- (1 '-Methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4 (1-Ethoxyethoxy) styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4- Vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2- Methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl- Methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- -Methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- ( 1-ethoxyethoxy) styrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) ) -4-Vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] ), Poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-styrene-co- [2- [O- 1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((1-methyladamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene- Co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxy) Ethoxy) styrene-co-2,3,4,5,6-pentafluorostyrene-co- [2- [O- (1′-methylpropylidene B) Carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5, 6-pentafluorostyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co -4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5,6-pentafluorostyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl -Methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-2,3,4,5,6-pentafluoro Styrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate- Co-4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [O- (1'-methyl Propylideneamino) carboxyamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-2,3 4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate ]), Poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl) -Methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [O- (1'-methylpropylideneamino) carboxy] Amino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene Co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4 -(1-ethoxyethoxy) styrene-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-methyl-2- Adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] ), Poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-methoxystyrene) -[2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxy Ethoxy) styrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((1-methyladamantyl) -4- Vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), Poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-styrene-co- [2- [1 '-(3', 5'- Methylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene- Co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1 -Ethoxyethoxy) styrene-co-2,3,4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazo L) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5, 6-pentafluorostyrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-methyl-2-adamantyl) -4-vinylbenzoate -Co-4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) Carbonylamino] ethyl-methacrylate]), poly (tertiary-butyl-4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-2,3,4,5,6-pentaph Orostyrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly ((2-tetrahydropyranyl) -4-vinyl Benzoate-co-4- (1-ethoxyethoxy) styrene-co-4-2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [1 '-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), and poly ((2-methyl-2-adamantyl) -4-vinylbenzoate-co-4- (1-ethoxyethoxy) styrene-co-4 -2,3,4,5,6-pentafluorostyrene-co-4-methoxystyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl -Methacrylate]).

  The organic thin film transistor insulating layer material of the present invention includes a compound (B) that is capable of generating an acid upon irradiation with electromagnetic waves or electron beams and has a thermal decomposition temperature of 200 ° C. or lower. Thermal decomposition here means generating an acid by heating.

  In general, electromagnetic waves include infrared rays, visible rays, ultraviolet rays and the like. A preferred electromagnetic wave is ultraviolet light. More preferable electromagnetic waves are ultraviolet rays having a wavelength of 450 nm or less, preferably 200 to 410 nm. If the wavelength of the ultraviolet ray is too short, the electromagnetic wave may not reach the interface between the base material and the insulating layer. If it is too long, the compound (B) may not be decomposed and developed.

  Although the thermal decomposition temperature of the said compound is 200 degrees C or less, Preferably it is 100-200 degreeC, More preferably, it is 120-200 degreeC. When the thermal decomposition temperature of the compound exceeds 200 ° C., formation of a crosslinked structure may be insufficient.

  Examples of the compound (B) include a toluenesulfonic acid ester compound and a triazine compound.

  Examples of the toluenesulfonic acid ester compound include α- (p-toluenesulfonyloxymethyl) benzoin, α- (p-toluenesulfonyloxy) -o-nitrotoluene, and α- (p-toluenesulfonyloxy) -p-nitrotoluene. Is mentioned.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6-methyl-1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6-phenyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4′-methoxyphenyl) -1,3,5-triazine, and 2,4-bis (trichloromethyl) -6- (3 ′, 4′-dimethoxyphenyl) -1,3,5-triazine may be mentioned.

  As the compound (B) that generates an acid of the present invention, a compound that generates an acid upon irradiation with electromagnetic waves or electron beams having a thermal decomposition temperature higher than 200 ° C. and a thermal acid generator having a thermal decomposition temperature of 200 ° C. or lower are combined. Can be used. The function of generating an acid by irradiation with electromagnetic waves or electron beams and the function of generating an acid when heated to a predetermined temperature, for example, 100 ° C. or more, are sufficient if the organic thin film transistor insulating layer material is provided. This is because it is not necessary for this compound to be provided.

<Organic thin film transistor insulating layer material>
The organic thin film transistor insulating layer material of the present invention may contain a solvent, an additive and the like for mixing and viscosity adjustment. Examples of the solvent 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, a sensitizer, a leveling agent, a viscosity modifier, etc. can be used.

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

  The organic thin film transistor insulating layer material of the present invention includes a polymer compound (A) containing a repeating unit represented by the formula (1), thereby leaking an organic thin film transistor having an insulating layer formed from the organic thin film transistor insulating layer material. The current is reduced.

<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.

  The formation of the gate insulating layer or overcoat layer is, for example, by preparing an organic thin film transistor insulating layer material (insulating layer coating solution) containing the polymer compound (A), the compound (B) and an organic solvent, and then insulating layer coating solution. Is applied to a substrate, dried, selectively irradiated with an electromagnetic wave or an electron beam through a mask, heat-treated, and then the irradiated portion is developed with an alkali developer, and the unirradiated portion is heated and cured.

  Here, the “base material” refers to a constituent member of the organic thin film transistor on which the organic thin film transistor insulating layer is disposed.

  The organic solvent used in the insulating layer coating solution is not particularly limited as long as it dissolves the polymer compound (A) and the compound (B). However, the organic solvent has a boiling point of 100 ° C. to 200 ° C. at normal pressure. Is preferred. Examples of organic solvents having a boiling point of 100 ° C. to 200 ° C. at normal pressure 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 insulating layer coating solution can be applied onto the organic semiconductor compound layer or the gate electrode by a known method such as spin coating, die coater, screen printing, or ink jet. The formed coating layer is dried as necessary. Drying here means removing the solvent contained in the applied resin composition.

  The dried coating layer is then selectively irradiated with electromagnetic waves or electron beams through a mask. The mask is a member having a transmission part that transmits electromagnetic waves or electron beams and a blocking part that blocks electromagnetic waves or electron beams. As for the mask used here, the part which interrupts electromagnetic waves or an electron beam has a shape corresponding to the part which wants to form an insulating layer among the surfaces of a base material.

  In the coating layer corresponding to the transmission part of the mask, the compound (B) that generates an acid is decomposed by irradiation with an electromagnetic wave or an electron beam to generate an acid, and the polymer compound (A) and the polymer compound are generated. A group that can be eliminated by the action of an acid in (A-1) is eliminated, and an alkali-soluble group is produced. The elimination reaction is promoted by heat. By immersing the coating layer in an alkaline developer, the portion irradiated with the electromagnetic wave or the electron beam is dissolved and removed, and a pattern having a shape corresponding to the blocking portion of the mask is transferred to the coating layer.

  The organic thin film transistor insulating layer material of the present invention has photosensitivity, and a pattern can be formed on a coating layer obtained by coating and drying the insulating layer coating solution. Since the coating layer is in a state where the organic thin film transistor insulating layer material is not yet crosslinked in the layer and is easily dissolved, a fine pattern can be formed with high accuracy and in a short time.

  The photosensitivity of the organic thin film transistor insulating layer material of the present invention is positive. An alkaline solution is used as a developer for developing the coating layer. As the alkaline solution, an alkaline developer usually used for developing a positive resist may be used.

  Specifically, the alkaline solution is a solution in which an alkaline salt is dissolved in an aqueous medium. The alkaline solution has a pH of 10 or more, preferably a pH of 10 to 14, more preferably a pH of 11 to 14.

  The aqueous medium refers to water or a solvent containing water and a water-soluble organic solvent. Water-soluble organic solvents include acetone, methanol, ethanol, isopropanol, tetrahydrofuran and the like. The content of the water-soluble organic solvent in the aqueous medium is 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less.

  As the alkaline salt, tetramethylammonium hydroxide (TMAH), monoethanolamine, sodium hydroxide, potassium hydroxide, potassium carbonate and the like are usually used.

  The coating layer to which the mask pattern has been transferred is cured by heating. By heating to a temperature equal to or higher than the thermal decomposition temperature of the compound (B) that generates an acid, the compound (B) that generates an acid is thermally decomposed to generate an acid, and the polymer compound (A) and the polymer compound ( A group that can be eliminated by the action of an acid in A-1) is eliminated, and an alkali-soluble group is produced. The alkali-soluble group has active hydrogen. Moreover, the 2nd functional group which reacts with active hydrogen produces | generates from the 1st functional group in a high molecular compound (A) and a high molecular compound (A-1) by heating, it reacts with this alkali-soluble group, and is bridge | crosslinked. A structure is formed.

One aspect of the method for forming the organic thin film transistor insulating layer of the present invention is:
Applying a liquid containing an organic thin film transistor insulating layer material to a substrate to form a coating layer on the substrate;
Irradiating a part of the coating layer with an electromagnetic wave or an electron beam through a mask;
Developing a portion of the coating layer irradiated with electromagnetic waves or electron beams to form a pattern on the coating layer;
as well as,
Applying heat to the coating layer on which the pattern is formed;
The manufacturing method of the organic thin-film transistor insulating layer containing this. Here, the development means that a portion of the coating layer having a shape corresponding to the transmission portion of the mask is dissolved and removed, and a portion of the shape corresponding to the blocking portion of the mask is left.

  The wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 200 to 410 nm. When the wavelength of the electromagnetic wave to be irradiated exceeds 450 nm, the decomposition of the compound (B) that generates an acid becomes insufficient, the solubility in an alkali developer becomes insufficient, and pattern formation may not be possible. 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.

  When applying heat to the coating layer, the coating layer is heated to a temperature equal to or higher than the thermal decomposition temperature of the acid-generating compound (B) and maintained for about 5 to 120 minutes, preferably about 10 to 60 minutes. Generally, the heating temperature of the coating layer is about 80 to 250 ° C, preferably about 100 to 230 ° C. If the heating temperature is too low or the heating time is too short, the insulating layer may be insufficiently crosslinked, and if the heating temperature is too high or the heating time is too long, the insulating layer may be damaged.

  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.

  For example, the organic semiconductor layer is formed by adding a solvent to the organic semiconductor compound to prepare an organic semiconductor coating solution, applying the organic semiconductor coating solution on the gate insulating layer, and drying the organic semiconductor coating solution. Do. In the present invention, the resin constituting the gate insulating layer has a benzene ring and has an affinity for an organic semiconductor compound. Therefore, a uniform and flat interface is formed between the organic semiconductor layer and the gate insulating layer by the coating and drying method.

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

  The organic thin film transistor of the present invention may be coated with an overcoat material for the purpose of protecting the organic thin film transistor and 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 Compound 1)
A Jimroth with a three-way cock attached to the top was attached to a 200 ml three-necked flask, and 25.45 g of 4-vinylbenzoic acid (manufactured by Aldrich) and 3,4-dihydro-2H-pyran were added to the three-necked flask. 50 g, a catalytic amount of concentrated hydrochloric acid and a stirring bar were added, and the air inside the flask was replaced with nitrogen. The flask was immersed in a 50 ° C. oil bath and reacted for 2 hours while stirring with a magnetic stirrer. After completion of the reaction, the reaction mixture was transferred to a 300 ml separatory funnel, 100 ml of diethyl ether was added, an aqueous sodium hydroxide solution was added, the organic layer was washed with water until the aqueous layer became alkaline, and the organic layer was separated. The organic layer was washed three times with 50 ml of ion exchange water, and then the organic layer was separated and dried by adding anhydrous magnesium sulfate. After anhydrous magnesium sulfate was filtered off, the filtrate was concentrated using a rotary evaporator to obtain Compound 1 as a colorless and transparent liquid. The yield of Compound 1 was 38.25 g, and the yield was 96%.

化合物１

Compound 1

Synthesis example 2
(Synthesis of polymer compound 1)
In a 50 ml pressure-resistant container (manufactured by ACE), 4.00 g of compound 1, 0.72 g of styrene (manufactured by Wako Pure Chemical Industries), 2- (O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate (Showa) 2.48 g of trade name “Karenz MOI-BM” manufactured by Denko, 0.04 g of 2,2′-azobis (2-methylpropionitrile), 24.11 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry) Then, argon gas was bubbled in order to purge dissolved oxygen, and then sealed, and polymerized in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 1 was dissolved. Polymer compound 1 has the following repeating units, and the numbers in parentheses indicate the mole fraction of the repeating units. There.

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 93000 (GPC made from Shimadzu, 1 Tskel super HM-H + 1 Tskel super H2000, mobile phase = THF).

Synthesis example 3
(Synthesis of polymer compound 2)
In a 50 ml pressure-resistant container (manufactured by Ace), 3.00 g of compound 1, 1.79 g of styrene (manufactured by Wako Pure Chemical Industries), 2- (O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate (Showa) 3.10 g of trade name “Karenz MOI-BM” manufactured by Denko, 0.04 g of 2,2′-azobis (2-methylpropionitrile), 18.51 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry) Then, argon gas was bubbled in order to purge dissolved oxygen and sealed, and polymerized in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 2 was dissolved. Polymer compound 2 has the following repeating units, and the numbers in parentheses indicate the mole fraction of the repeating units. There.

高分子化合物２

Polymer compound 2

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 2 was 97000 (GPC made from Shimadzu, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Synthesis example 4
(Synthesis of polymer compound 3)
In a 50 ml pressure-resistant container (manufactured by Ace), 3.00 g of compound 1, 0.46 g of acrylonitrile (manufactured by Wako Pure Chemical Industries), 2- (O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate (Showa) 3.10 g of trade name “Karenz MOI-BM” manufactured by Denko Co., Ltd.), 1.16 g of 4-methoxystyrene (manufactured by Tokyo Chemical Industry), 0.04 g of 2,2′-azobis (2-methylpropionitrile), 18.08 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and argon gas was bubbled in order to purge dissolved oxygen, which was then sealed and polymerized in an oil bath at 80 ° C. for 8 hours to dissolve polymer compound 3. A viscous propylene glycol monomethyl ether acetate solution was obtained. Subscript numbers to have. Parentheses represents the mole fraction of repeating units.

高分子化合物３

Polymer compound 3

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 3 was 88000 (Shimadzu GPC, 1 Tskel super HM-H + 1 Tskel super H2000, mobile phase = THF).

Synthesis example 5
(Synthesis of polymer compound 4)
In a 50 ml pressure-resistant container (manufactured by Ace), 3.00 g of compound 1, 3.34 g of 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich), 2- (O- [1′-methylpropylidene) 3.10 g of amino] carboxyamino] ethyl-methacrylate (made by Showa Denko, trade name “Karenz MOI-BM”), 0.05 g of 2,2′-azobis (2-methylpropionitrile), propylene glycol monomethyl ether 22.14 g of acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and argon gas was bubbled in order to purge dissolved oxygen, and then sealed, and the polymer compound 4 was dissolved in an oil bath at 80 ° C. for 8 hours. A viscous propylene glycol monomethyl ether acetate solution was obtained, and the polymer compound 4 had the following repeating units. For example numerals indicate the mole fraction of repeating units.

高分子化合物４

Polymer compound 4

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 4 was 85000 (GPC made from Shimadzu, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Synthesis Example 6
(Synthesis of polymer compound 5)
In a 50 ml pressure-resistant container (manufactured by Ace), 3.00 g of compound 1, 1.71 g of tertiary-butoxystyrene (manufactured by Wako Pure Chemical Industries), 2- (O- [1′-methylpropylideneamino] carboxyamino] ethyl -1.55 g of methacrylate (manufactured by Showa Denko, trade name “Karenz MOI-BM”), 0.43 g of 4-methoxystyrene (manufactured by Tokyo Chemical Industry), and 2,2′-azobis (2-methylpropionitrile) 0.03 g and 15.69 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and argon gas was bubbled in order to purge dissolved oxygen, which was then sealed and polymerized in an oil bath at 80 ° C. for 8 hours. A viscous propylene glycol monomethyl ether acetate solution in which compound 5 was dissolved was obtained. Ri returns has a unit. Subscript numbers in parentheses indicate the molar fraction of the repeating units.

高分子化合物５

Polymer compound 5

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 5 was 91000 (Shimadzu GPC, 1 Tskel super HM-H + 1 Tskel super H2000, mobile phase = THF).

Synthesis example 7
(Synthesis of polymer compound 6)
In a 50 ml pressure vessel (made by Ace), 2.00 g of compound 1, 0.83 g of 4- (1-ethoxyethoxy) styrene (manufactured by Tosoh Organic Chemical), 2- (O- [1′-methylpropylideneamino] Carboxyamino] ethyl-methacrylate (Showa Denko, trade name “Karenz MOI-BM”) 1.03 g, 4-methoxystyrene (Tokyo Kasei) 0.58 g, 2,2′-azobis (2-methylpro 0.02 g of pionitrile) and 10.41 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), bubbled with argon gas to purge dissolved oxygen, and sealed in an oil bath at 80 ° C. for 8 hours. As a result, a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 6 was dissolved was obtained. 6 has the following repeating units. The subscript numbers of parentheses indicates the mole fraction of the repeating unit.

高分子化合物６

Polymer compound 6

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 6 was 78000 (GPC made from Shimadzu, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Synthesis example 8
(Synthesis of polymer compound 7)
In a 50 ml pressure vessel (made by Ace), 2.00 g of 2-methyl-2-adamantyl methacrylate synthesized from 2-methyl-2-adamantanol and methacryloyl chloride, α synthesized from α-hydroxy-γ-butyrolactone and methacryloyl chloride -2.13 g of methacryloyloxy-γ-butyrolactone, 0.37 g of 2-hydroxyethyl methacrylate, 2- (O- [1′-methylpropylideneamino] carboxyamino] ethyl methacrylate (made by Showa Denko, trade name “ 0.75 g of Karenz MOI-BM ", 0.03 g of 2,2'-azobis (2-methylpropionitrile), and 14.63 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry), purged with dissolved oxygen Bubbling argon gas to The polymer compound was polymerized in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 7 was dissolved. The number in parentheses indicates the mole fraction of repeating units.

高分子化合物７

Polymer compound 7

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 7 was 501000 (Shimadzu GPC, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Example 1
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of polymer compound 1 obtained in Synthesis Example 2 and 0.003 g of the following compound (“MBZ-101” manufactured by Midori Chemical) as a photoacid generator Then, 1.00 g of propylene glycol monomethyl ether acetate was added and dissolved while stirring to prepare a uniform coating solution 1 as an organic thin film transistor insulating layer material.

  The thermal decomposition starting temperature of MBZ-101 measured using TG-DTA (“DTG-60” manufactured by Shimadzu Corporation) was 177 ° C.

The obtained coating solution 1 is filtered using a membrane filter having a pore size of 0.45 μm, spin-coated on a glass substrate with a chromium electrode, and then dried on a hot plate at 100 ° C. for 1 minute to form a coating layer. did. Thereafter, the coating layer was irradiated with UV light (wavelength 365 nm) of 1200 mJ / cm ² through a mask using an aligner (manufactured by Canon; PLA-521), post-baked at 100 ° C. for 30 seconds on a hot plate, and then a negative positive developer. It was immersed in NPD-18 for 30 seconds to remove the exposed portion and developed. The developed glass substrate was washed with ion-exchanged water, dried with a spin dryer, and then baked on a hot plate at 220 ° C. for 30 minutes in nitrogen to obtain a gate insulating layer having a via hole.

  Forming a via hole in an insulating layer using the organic thin film transistor insulating layer material of the present invention, applying a liquid containing a resist material on the insulating layer, forming a resist layer, exposing the resist layer through a mask The step of developing the resist layer to form a pattern of the resist layer, the step of transferring the pattern to the insulating layer using the resist layer on which the pattern is formed as a mask, and the step of peeling and removing the resist layer on which the pattern is formed are omitted. And via holes can be easily formed.

  Next, an aluminum electrode was formed on the obtained gate insulating layer by metal mask vapor deposition to produce a MIM (Metal Insulator Metal) element.

<Evaluation of electrical characteristics of MIM element>
For the MIM element thus fabricated, an electric field of 1 MV / cm was applied between the electrodes, and the leakage current was measured using a vacuum probe (BCT22MDC-5-HT-SCU; manufactured by Nagase Electronic Equipments Service Co., LTD). . The results are shown in Table 1.

<Evaluation of resist characteristics of organic thin film transistor insulating layer material>
The resist characteristics of the organic thin film transistor insulating layer material were evaluated by whether or not a 25 μm square pattern was resolved. The case where it was resolved was represented by “◯”, and the case where it was not resolved was represented by “×”.

Example 2
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of polymer compound 2 obtained in Synthesis Example 3, 0.003 g of MBZ-101 (manufactured by Midori Chemical) as a photoacid generator, propylene glycol monomethyl 1.00 g of ether acetate was added and dissolved while stirring to prepare a uniform coating solution 3 as an organic thin film transistor insulating layer material.

  An MIM element was prepared in the same manner as in Example 1 except that the coating solution 3 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Example 3
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of polymer compound 3 obtained in Synthesis Example 4, 0.003 g of MBZ-101 (manufactured by Midori Chemical) as a photoacid generator, propylene glycol monomethyl 1.00 g of ether acetate was added and dissolved while stirring to prepare a uniform coating solution 4 as an organic thin film transistor insulating layer material.

  An MIM element was prepared in the same manner as in Example 1 except that the coating solution 4 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Example 4
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 5 obtained in Synthesis Example 6, 0.003 g of MBZ-101 (manufactured by Midori Chemical) as a photoacid generator, propylene glycol monomethyl 1.00 g of ether acetate was added and dissolved while stirring to prepare a uniform coating solution 5 as an organic thin film transistor insulating layer material.

  An MIM element was prepared in the same manner as in Example 1 except that the coating solution 5 was used instead of the coating solution 1, and leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Example 5
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 6 obtained in Synthesis Example 7, 0.003 g of MBZ-101 (manufactured by Midori Chemical) as a photoacid generator, propylene glycol monomethyl 1.00 g of ether acetate was added and dissolved while stirring to prepare a uniform coating solution 6 as an organic thin film transistor insulating layer material.

  An MIM element was produced in the same manner as in Example 1 except that the coating solution 6 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Example 6
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 5 obtained in Synthesis Example 6 and 0.20 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 4 obtained in Synthesis Example 5; Add 0.0035 g of MBZ-101 (manufactured by Midori Kagaku), a photoacid generator, and 1.00 g of propylene glycol monomethyl ether acetate, dissolve with stirring to obtain a uniform coating solution 7 that is an organic thin film transistor insulating layer material. Prepared.

  An MIM element was prepared in the same manner as in Example 1 except that the coating solution 7 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Example 7
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 6 obtained in Synthesis Example 7 and 0.20 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 4 obtained in Synthesis Example 5; Add 0.0035 g of MBZ-101 (manufactured by Midori Kagaku), a photoacid generator, and 1.00 g of propylene glycol monomethyl ether acetate, dissolve with stirring to obtain a uniform coating solution 8 that is an organic thin film transistor insulating layer material. Prepared.

  An MIM element was produced in the same manner as in Example 1 except that the coating solution 8 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. The results are shown in Table 1.

Comparative Example 1
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 1.00 g of a propylene glycol monomethyl ether acetate solution of the polymer compound 7 obtained in Synthesis Example 8, 0.003 g of MBZ-101 (manufactured by Midori Chemical) as a photoacid generator, propylene glycol monomethyl 1.00 g of ether acetate was added and dissolved while stirring to prepare a uniform coating solution 9 as an organic thin film transistor insulating layer material.

  An MIM element was prepared in the same manner as in Example 1 except that the coating solution 9 was used instead of the coating solution 1, and the leakage current and resist characteristics were evaluated. 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 (11)

Repeating unit and formula containing the following first functional group in the molecule

(1)
[Wherein, R ₁ 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 n represents an integer of 1 to 5. ]
A polymer compound (A) containing a repeating unit represented by:
A compound capable of generating an acid upon irradiation with an electromagnetic wave or an electron beam and having a thermal decomposition temperature of 200 ° C. or lower, (B)
Including organic thin film transistor insulating layer material.
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.   2. The organic thin film transistor insulating layer according to claim 1, wherein the first functional group is at least one group selected from the group consisting of an isocyanato group blocked with a blocking agent and an isothiocyanate group blocked with a blocking agent. material. The isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula

(3)
[Wherein, Xa represents an oxygen atom or a sulfur atom, and R ₆ and R ₇ 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 2, which is a group represented by: The isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are represented by the formula

(4)
[Wherein, Xb represents an oxygen atom or a sulfur atom, and R ₈ , 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 2, which is a group represented by: The polymer compound (A) further has the formula

(2)
[Wherein R ₂ represents a hydrogen atom or a methyl group. 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 an organic group that can be eliminated 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. b represents an integer of 0 or 1, and m represents an integer of 1 to 5. ]
The organic thin film transistor insulating layer material according to any one of claims 1 to 4, which is a polymer compound (A-1) having a repeating unit represented by: The process of apply | coating the liquid containing the organic thin-film transistor insulating-layer material as described in any one of Claims 1-5 to a base material, and forming a coating layer on this base material;
Irradiating a part of the coating layer with an electromagnetic wave or an electron beam through a mask;
Developing a portion of the coating layer irradiated with electromagnetic wave or electron beam to form a pattern on the coating layer; and
Applying heat to the coating layer on which the pattern is formed;
The manufacturing method of the organic thin-film transistor insulating layer containing this.   The method for producing an organic thin film transistor insulating layer according to claim 6, wherein the electromagnetic wave is ultraviolet light.   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 1-5.   The organic thin film transistor according to claim 8, wherein the organic thin film transistor insulating layer is a gate insulating layer.   A display member comprising the organic thin film transistor according to claim 8.   A display comprising the display member according to claim 10.

Images