JPWO2017141933A1 - Polymer compound, composition and organic thin film transistor - Google Patents

Abstract

Organic thin film transistor with higher carrier mobility. A repeating unit having at least one group selected from the group comprising a blocked isocyanato group and a blocked isothiocyanato group, a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group A polymer compound comprising at least one repeating unit selected from the group comprising, and a repeating unit represented by the formula (1). (In the formula (1), R1, R2, and R3 each represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms, and R4 represents a hydrogen atom, a chlorine atom, a bromine atom, or iodine. An atom and a monovalent organic group having 1 to 20 carbon atoms, Rf represents a fluorine atom and a monovalent organic group containing a fluorine atom, Ra represents a divalent organic group having 1 to 20 carbon atoms,- O-, -CO-, -COO-, -NHCO-, -NHCOO- are represented, m1 represents an integer of 0 to 6, and n1 represents an integer of 1 to 5.)

Description

  The present invention relates to a polymer compound and a composition containing the polymer compound, and more particularly to a composition for an insulating layer of an organic thin film transistor and an organic thin film transistor including a gate insulating layer using the composition as a material.

  An organic thin film field effect transistor (organic thin film transistor) using an organic material can be manufactured by a lower temperature manufacturing process than an inorganic field effect transistor using an inorganic material. Therefore, in an organic thin film transistor, a plastic substrate or a plastic film can be used as a substrate, and as a result, a lighter and less fragile transistor can be manufactured.

  An organic thin film transistor may be manufactured by applying or printing a liquid (solution, dispersion) containing an organic material. In this case, a large area organic thin film transistor array can be manufactured at low cost. is there.

  Furthermore, there are a wide variety of materials that can be used for the organic thin film transistor. Therefore, the characteristics of the organic thin film transistor can be fundamentally changed by appropriately selecting and using various materials having different molecular structures. Therefore, by appropriately combining materials having different functions, it is also possible to realize an electronic device including organic thin film transistors having various functions that are impossible with a field effect transistor using an inorganic material.

  In a field effect transistor, a voltage (gate voltage) applied to a gate electrode acts on a semiconductor layer through a gate insulating layer to control on / off of a drain current. Therefore, the material of the gate insulating layer used for the organic thin film transistor is required to have a high dielectric breakdown strength when it is formed into a thin film.

  In particular, in the case of a bottom gate type organic thin film transistor, the organic semiconductor layer is provided so as to overlap the gate insulating layer. Therefore, the material of the gate insulating layer is different from the organic semiconductor layer in order to form a good interface with the organic semiconductor layer. High affinity is required.

  Until now, various materials have been studied for the material of the gate insulating layer used in the organic thin film transistor.

  For example, Patent Document 1 below describes a thermosetting resin composition containing fluorine atoms as a material for a gate insulating layer in an organic thin film transistor. Patent Document 1 below shows that an organic thin film transistor including a gate insulating layer formed using this material has low hysteresis and stable electrical characteristics.

Patent No. 5479817

  However, considering that the organic thin film transistor is used as a driving element for driving a light emitting element such as an organic electroluminescence element (organic EL element), it is necessary to further improve the carrier mobility of the organic thin film transistor.

  Accordingly, an object of the present invention is to provide an organic thin film transistor having higher carrier mobility.

（式（１）中、
Ｒ^１、Ｒ^２、Ｒ^３は、互いに異なっていてもよく、水素原子、フッ素原子、又は炭素原子数１〜２０の１価の有機基を表す。
Ｒ^４は、水素原子、塩素原子、臭素原子、ヨウ素原子又は炭素原子数１〜２０の１価の有機基を表す。
Ｒｆは、フッ素原子、又はフッ素原子を含む１価の有機基を表す。
Ｒ^ａは、炭素原子数１〜２０の２価の有機基、−Ｏ−で表される基、−ＣＯ−で表される基、−ＣＯＯ−で表される基、−ＮＨＣＯ−で表される基、又は−ＮＨＣＯＯ−で表される基を表し、前記−Ｏ−で表される基、前記−ＣＯ−で表される基、前記−ＣＯＯ−で表される基、前記−ＮＨＣＯ−で表される基、及び前記−ＮＨＣＯＯ−で表される基の結合手は、前記式（１）中の前記Ｒ^１が結合する炭素原子側に位置していても、前記式（１）中のベンゼン環を構成する炭素原子側に位置していてもよく、前記２価の有機基中の水素原子は、フッ素原子で置換されていてもよい。
ｍ１は、０〜６の整数を表す。
ｎ１は、１〜５の整数を表す。
Ｒ^ａが複数個ある場合、それらは互いに異なっていてもよい。Ｒ^４が複数個ある場合、それらは互いに異なっていてもよい。Ｒｆが複数個ある場合、それらは互いに異なっていてもよい。）
［２］ 前記ヒドロキシ基を有する繰り返し単位及びカルボキシ基を有する繰り返し単位が、下記式（２）で表される繰り返し単位である、［１］に記載の高分子化合物。

（式（２）中、
Ｒ^５、Ｒ^６、Ｒ^７は、互いに異なっていてもよく、水素原子、フッ素原子、又は炭素原子数１〜２０の１価の有機基を表す。Ｒ^ｂは、炭素原子数１〜２０の２価の有機基、−Ｏ−で表される基、−ＣＯ−で表される基、−ＣＯＯ−で表される基、−ＮＨＣＯ−で表される基、又は−ＮＨＣＯＯ−で表される基を表し、前記−Ｏ−で表される基、前記−ＣＯ−で表される基、前記−ＣＯＯ−で表される基、前記−ＮＨＣＯ−で表される基、及び前記−ＮＨＣＯＯ−で表される基の結合手は、前記式（２）中の前記Ｒ^５が結合する炭素原子側に位置していても、前記式（２）中のＸ^ａ側に位置していてもよい。前記２価の有機基中の水素原子は、フッ素原子で置換されていてもよい。
ｍ２は、０〜６の整数を表す。
Ｘ^ａは、ヒドロキシ基又はカルボキシ基を表す。）
［３］ 前記ブロック化イソシアナト基又はブロック化イソチオシアナト基が、下記式（３）で表される基又は下記式（４）で表される基である、［１］又は［２］に記載の高分子化合物。

（式（３）及び（４）中、
Ｘ^ｂは、酸素原子又は硫黄原子を表す。
Ｒ^８〜Ｒ^１２は、互いに異なっていてもよく、水素原子又は炭素原子数１〜２０の１価の有機基を表す。）
［４］ ［１］〜［３］のいずれか一つに記載の高分子化合物を含む組成物。
［５］ ［１］〜［３］のいずれか一つに記載の高分子化合物及び有機溶媒のみからなる、［４］に記載の組成物。
［６］ ［４］又は［５］に記載の組成物からなる有機薄膜トランジスタの絶縁層用組成物。
［７］ ［４］〜［６］のいずれか一つに記載の組成物を硬化した膜。
［８］ ［７］に記載の膜をゲート絶縁層として含む、有機薄膜トランジスタ。
［９］ ［７］に記載の膜をオーバーコート層としてさらに含む、［８］に記載の有機薄膜トランジスタ。
［１０］ ［４］〜［６］のいずれか一つに記載の組成物を、基材の表面に塗布して塗布層を形成する工程と、
前記塗布層を硬化する工程と
を含む、有機薄膜トランジスタの製造方法。That is, the present invention provides the following [1] to [10].
[1] A repeating unit having at least one group selected from the group comprising a blocked isocyanato group and a blocked isothiocyanato group;
At least one repeating unit selected from the group comprising a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group;
The high molecular compound containing the repeating unit represented by following formula (1).

(In the formula (1),
R ¹ , R ² , and R ³ may be different from each other, and represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms.
R ⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or a monovalent organic group having 1 to 20 carbon atoms.
Rf represents a fluorine atom or a monovalent organic group containing a fluorine atom.
R ^a is represented by a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond represented by the group represented by the group represented by -NHCOO- is located on the carbon atom side to which R ¹ in the formula (1) is bonded, the group represented by the formula (1) It may be located on the carbon atom side constituting the benzene ring, and the hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
m1 represents the integer of 0-6.
n1 represents the integer of 1-5.
When there are ^a plurality of R ^{a s} , they may be different from each other. When there are a plurality of R ⁴ , they may be different from each other. When there are a plurality of Rf, they may be different from each other. )
[2] The polymer compound according to [1], wherein the repeating unit having a hydroxy group and the repeating unit having a carboxy group are repeating units represented by the following formula (2).

(In the formula (2),
R ⁵ , R ⁶ , and R ⁷ may be different from each other, and represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms. R ^b is a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond of the group represented by the group represented by —NHCOO— is located on the carbon atom side to which R ⁵ in the formula (2) is bonded, the group in the formula (2) It may be located on the ^Xa side. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
m2 represents the integer of 0-6.
^Xa represents a hydroxy group or a carboxy group. )
[3] The high blocked structure according to [1] or [2], wherein the blocked isocyanato group or blocked isothiocyanato group is a group represented by the following formula (3) or a group represented by the following formula (4): Molecular compound.

(In the formulas (3) and (4),
^Xb represents an oxygen atom or a sulfur atom.
R ^{8 to} R ¹² may be different from each other and represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. )
[4] A composition comprising the polymer compound according to any one of [1] to [3].
[5] The composition according to [4], comprising only the polymer compound according to any one of [1] to [3] and an organic solvent.
[6] A composition for an insulating layer of an organic thin film transistor, comprising the composition according to [4] or [5].
[7] A film obtained by curing the composition according to any one of [4] to [6].
[8] An organic thin film transistor comprising the film according to [7] as a gate insulating layer.
[9] The organic thin film transistor according to [8], further including the film according to [7] as an overcoat layer.
[10] A step of applying the composition according to any one of [4] to [6] to a surface of a substrate to form a coating layer;
A method for producing an organic thin film transistor, comprising: curing the coating layer.

  When the polymer compound of the present invention and the composition containing the polymer compound are used, the carrier mobility of the organic thin film transistor can be further increased.

FIG. 1 is a schematic view schematically showing the structure of a bottom gate top contact type organic thin film transistor according to a first embodiment of the present invention. FIG. 2 is a schematic view schematically showing the structure of a bottom gate bottom contact type organic thin film transistor according to a second embodiment of the present invention. FIG. 3 is a schematic view schematically showing the structure of a top gate bottom contact type organic thin film transistor according to a third embodiment of the present invention.

  Next, embodiments of the present invention will be described in more detail. Each drawing referred to only schematically shows the shape, size, and arrangement of components to the extent that the invention can be understood. The present invention is not limited to the following description, and each component can be appropriately changed without departing from the gist of the present invention. In the drawings used for the description, the same components are denoted by the same reference numerals, and overlapping descriptions may be omitted. Further, the configuration according to the embodiment of the present invention is not necessarily manufactured or used in the arrangement shown in the drawings.

  In the present specification, the “polymer compound” means a compound containing a plurality of structural units (repeating units) which may be different from each other in the molecule. "include. In the present specification, the “low molecular weight compound” means a compound that does not contain a plurality of structural units in the molecule.

<Explanation of common terms>
Terms commonly used in this specification have the following meanings unless otherwise specified.

  The “monovalent organic group having 1 to 20 carbon atoms” may be linear, branched, or cyclic, and may be saturated or unsaturated.

  Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and 3 to 20 carbon atoms. A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, Examples thereof include an alkoxycarbonyl group having 2 to 20 carbon atoms and an aryloxycarbonyl group having 7 to 20 carbon atoms, preferably a linear hydrocarbon group having 1 to 6 carbon atoms and 3 to 6 carbon atoms. Branched hydrocarbon group, cyclic hydrocarbon group having 3 to 6 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy having 6 to 20 carbon atoms Groups, acyl groups of 2 to 7 carbon atoms, carbon atoms 2-7 alkoxycarbonyl group, and the like aryloxycarbonyl group having 7 to 20 carbon atoms.

  Straight chain hydrocarbon group having 1 to 20 carbon atoms, branched hydrocarbon group having 3 to 20 carbon atoms, cyclic hydrocarbon group having 3 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon These groups include aryloxy groups having 6 to 20 atoms, acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, and aryloxycarbonyl groups having 7 to 20 carbon atoms. The hydrogen atom may be substituted with a halogen atom.

  In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with a monovalent organic group or a halogen atom.

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, tert-butyl group, and 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 , Pentaf Orofeniru group, trifluoromethylphenyl group, chlorophenyl group, bromophenyl group, a methoxy group, an ethoxy group, a phenoxy group, an acetyl group, a benzoyl group, a methoxycarbonyl group, and the like phenoxycarbonyl group.
As the monovalent organic group having 1 to 20 carbon atoms, an alkyl group is preferable.

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

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

  Specific examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, ethylenephenylene group, diethylenephenylene group, and triethylenephenylene group. , Propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, ethylanthrylene group, and the like.

  The “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

<Polymer compound>
The polymer compound of the present invention comprises a repeating unit having at least one group selected from the group comprising a blocked isocyanato group and a blocked isothiocyanato group, a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a hydroxy group And a polymer compound containing at least one repeating unit selected from the group containing a repeating unit having a carboxy group and a repeating unit represented by the following formula (1) (hereinafter referred to as “polymer compound (A)”). ").

In formula (1),
R ¹ , R ² , and R ³ may be different from each other, and represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms.
R ⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or a monovalent organic group having 1 to 20 carbon atoms.
Rf represents a fluorine atom or a monovalent organic group containing a fluorine atom.
R ^a is represented by a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond represented by the group represented by the group represented by -NHCOO- is located on the carbon atom side to which R ¹ in the formula (1) is bonded, the group represented by the formula (1) It may be located on the carbon atom side constituting the benzene ring, and the hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
m1 represents the integer of 0-6.
n1 represents the integer of 1-5.
When there are ^a plurality of R ^{a s} , they may be different from each other. When there are a plurality of R ⁴ , they may be different from each other. When there are a plurality of Rf, they may be different from each other.

(Polymer Compound (A))
Here, the polymer compound (A) will be described. The polymer compound (A) contains a blocked isocyanato group and / or a blocked isothiocyanato group, a hydroxy group and / or a carboxy group, and a repeating unit represented by the formula (1) in the same molecule.

  The polymer compound (A) has a blocked isocyanato group and / or a blocked isothiocyanato group in the molecule as described above.

  Here, when the blocked isocyanato group and / or the blocked isothiocyanato group possessed by the polymer compound (A) is a first functional group, the first functional group does not react with active hydrogen. However, when an electromagnetic wave or heat acts on the first functional group, a second functional group is generated, and the generated second functional group can react with active hydrogen. In other words, the first functional group is a functional group that can generate a second functional group that reacts with active hydrogen by elimination of the protective group derived from the blocking agent by the action of electromagnetic waves or heat. is there.

  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.

  From the viewpoint of maintaining the storage stability of the composition, the second functional group that reacts with active hydrogen is preferably protected (blocked) until the step of forming the gate insulating layer is performed. That is, the first functional group is preferably a functional group that generates a second functional group that reacts with active hydrogen by being removed by electromagnetic wave treatment or heat treatment in the step of forming the gate insulating layer. If it does in this way, it will exist in a composition as a 1st functional group until the formation process of a gate insulating layer is implemented, As a result, the storage stability of a composition improves.

  Since the polymer compound (A) has a blocked isocyanato group and / or a blocked isothiocyanate group, a hydroxy group and / or a carboxy group in the same molecule as described above, the polymer compound (A) Is highly crosslinkable, and when the composition containing the polymer compound (A) is cured to form a gate insulating layer (thin film), an uncrosslinked site is unlikely to remain, and polarization is difficult even when a gate voltage is applied. It is considered that the polarization of the gate insulating layer is suppressed. In this way, when the polarization of the gate insulating layer is suppressed, the carrier mobility is improved.

  In the polymer compound (A), the blocked isocyanato group and / or the blocked isothiocyanato group and the hydroxy group and / or the carboxy group have a molar ratio when the molar amount of the hydroxy group and / or the carboxy group is 100. , Preferably adjusted to be 1/100 to 10000/100, more preferably 10/100 to 1000/100.

  The polymer compound (A) preferably has a weight average molecular weight of 3,000 to 1,000,000, and more preferably 5,000 to 500,000. The polymer compound (A) may be any of linear, branched, and cyclic embodiments.

  The polymer compound (A) includes a repeating unit containing a fluorine atom. Therefore, the hydrophobicity of the cured product (film) obtained by curing the composition containing the polymer compound (A) can be improved.

  Examples of the polymer compound (A) include poly (styrene-co- (2,3,4,5,6-pentafluorostyrene) -co- [2- [O- (1′-methylpropylideneamino)]. Carboxyamino] ethyl-methacrylate] -co- (2-hydroxybutyl methacrylate)), poly (styrene-co- (2,3,4,5,6-pentafluorostyrene) -co- [2- [O- ( 1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-methacrylic acid), poly (styrene-co- (2,3,4,5,6-pentafluorostyrene) -co- [2- [ O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (2-hydroxybutyl methacrylate)), poly (styrene-co- (2,3,4) 5,6-pentafluorostyrene) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (4-vinylbenzoic acid)), poly ((2, 3,4,5,6-pentafluorobenzyl acrylate) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl methacrylate)), Poly (2,3,4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co- [2- (2 -Hydroxyethoxy) ethyl acrylate]), poly (2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co- [2- [O- (1 ' Methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (3-hydroxy-1-adamantyl acrylate)), poly (2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co- [ 2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co- (4-hydroxycyclohexyl acrylate)), poly (2,3,4,5,6-pentafluorostyrene -Co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co-acrylic acid), poly (2,3,4, 5,6-pentafluorostyrene-co-acrylonitrile-co- [2- [1 '-(3', 5 ' -Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co-ethylene glycol monoallyl ether), poly (styrene-co-2,3,4,5,6-pentafluorostyrene-co- [ 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (1,5-hexadiene-3,4-diol)), poly (styrene-co-2,3,4) , 5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-pentaerythritol triacrylate), poly (styrene-co- 2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co- [2- [O- (1'- Tylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (p-hydroxystyrene)), poly (styrene-co-2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co- [ 2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl acrylate)), poly (styrene-co-2,3,4,5,6) -Pentafluorostyrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co- (8-hydroxyoctyl methacrylate)) , Poly (styrene-co-2,3,4,5,6-pentafluorostyrene-co-acrylic Nitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co- [2- (2-hydroxyethoxy) ethyl methacrylate]) , Poly (methyl methacrylate-co-2,3,4,5,6-pentafluorostyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- ( 3-hydroxy-1-adamantyl methacrylate)), poly (methyl methacrylate-co-2,3,4,5,6-pentafluorostyrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) ) Carboxyamino] ethyl-methacrylate] -co- (4-hydroxymethylcyclohexyl acrylate)), poly ( 2,3,4,5,6-pentafluorostyrene-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl -Methacrylate] -co- (4-hydroxymethylcyclohexyl metallate)), poly (2,3,4,5,6-pentafluorostyrene-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co- (2-acryloyloxyethyl-succinic acid)), poly (styrene-co-2,3, 4,5,6-pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate -Co- (2-carboxyethyl acrylate)), poly (styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethyl) Pyrazolyl) carboxyamino] ethyl-methacrylate] -co- (4-carboxybutyl acrylate)), poly (styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2 -[O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (2-carboxybutyl methacrylate)), poly (styrene-co-2,3,4,5,6-pentafluoro Benzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyl Amino] ethyl-methacrylate] -co- (2-hydroxyethyl methacrylate)), poly (styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O -(1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co- (2-hydroxyethyl methacrylate)), poly (styrene-co-2,3,4,5,6) -Pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium-co-acrylic acid), poly (Methyl methacrylate-co-2,3,4,5,6-pentafluoro Robenzyl methacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (3-vinylbenzoic acid)), poly (methyl methacrylate-co-2,3 , 4,5,6-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-methacrylic acid), poly (styrene-co -2,3,4,5,6-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [O- (1'-methylpropylideneamino) carboxyamino ] Ethyl-methacrylate] -co-methacrylic acid), poly (styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate) Chlorate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-methacrylic acid), Poly (styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxylamino] ethyl-methacrylate] -co-methacrylic acid ), Poly (styrene-co-4- (1-ethoxyethyl) styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylidene) Amino) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl methacrylate)), poly (styrene-co-4- (1- Toxiethyl) styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl methacrylate)), poly (styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [ 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl methacrylate)), poly (styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) ) Benzoate} -co-2,3,4,5,6-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co- (4-hydroxybutyl methacrylate)) and the like.

(Method for producing polymer compound (A))
The polymer compound (A) has, for example, a monomer (polymerizable monomer) serving as a raw material of a repeating unit having at least one group selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group, and a hydroxy group A monomer (polymerizable monomer) serving as a raw material for at least one repeating unit selected from the group comprising a repeating unit, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group, and represented by the formula (1) Photopolymerization of a monomer (polymerizable monomer) that is a material of the repeating unit and another monomer (polymerizable monomer) that is a raw material of another repeating unit that can be included in the polymer compound (A) if necessary It can manufacture by the method of copolymerizing using an agent or a thermal-polymerization initiator.

  Examples of the photopolymerization initiator for polymerizing the monomer that is the material of the polymer compound (A) 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, ben Carbonyl compounds such as inoctyl ether, benzyldimethyl ketal, benzyl diethyl ketal, diacetyl, anthraquinones such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, thioxanthone derivatives, diphenyl disulfide, dithiocarbamate, etc. A sulfur compound is mentioned.

  The thermal polymerization initiator for polymerizing the monomer that is the material of the polymer compound (A) may be any radical polymerization initiator. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyrate. Ronitrile, 2,2′-azobisisovaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), 1,1′- Azo compounds such as azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylpropane), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide , Cyclohexanone peroxide, ketone peroxide such as acetylacetone peroxide, isobutyl peroxide, benzo Diacyl peroxides such as luperoxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, Hydroperoxides such as diisopropylbenzene peroxide, cumene hydroperoxide, tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, tris (tert-butylperoxy) triazine Dialkyl peroxides such as 1,1-di-tert-butylperoxycyclohexane, peroxyketals such as 2,2-di (tert-butylperoxy) butane, and tert-butylperoxypivale Tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy -3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, alkyl peresters such as di-tert-butylperoxytrimethyladipate, diisopropyl peroxydicarbonate, di-sec -Percarbonates such as butyl peroxydicarbonate and tert-butylperoxyisopropyl carbonate.

  Hereinafter, the repeating unit that the polymer compound (A) may contain will be described.

(Repeating unit having at least one group selected from the group comprising a blocked isocyanato group and a blocked isothiocyanato group)
The polymer compound (A) includes a repeating unit having at least one group selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group.
In other words, the polymer compound (A) may contain a blocked isocyanato group and a blocked isothiocyanato group, whether it contains a repeating unit having only a blocked isocyanato group or a repeating unit having only a blocked isothiocyanato group. Of repeating units having only a blocked isocyanato group, repeating units having only a blocked isothiocyanato group, and repeating units having both a blocked isocyanato group and a blocked isothiocyanato group. A combination of more than one species may be included.

The structure of the repeating unit having at least one group selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group is based on the chemical structure of the monomer as the raw material.
Hereinafter, examples of a monomer that is a raw material for a repeating unit having at least one group selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group will be shown.

  Examples of the monomer that is a raw material of the repeating unit having at least one group selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group include a blocked isocyanate group or a blocked isothiocyanate group and an unsaturated bond. The monomer which has in the inside is mentioned.

  A monomer having a blocked isocyanato group and / or a blocked isothiocyanato group and an unsaturated bond in the molecule reacts with the blocking agent and a compound having the isocyanato group and / or the isothiocyanato group and the unsaturated bond in the molecule. Can be manufactured. 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, 2- (2′-methacryloyloxyethyl) oxyethyl isocyanate, and the like. It is done. Examples of the compound having an unsaturated double bond and an isothiocyanato group in the molecule include 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, 2- (2′-methacryloyloxyethyl) oxyethyl isothiocyanate. Etc.

  Examples of the monomer having an unsaturated double bond and a blocked isocyanate group in the molecule include 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate, 2- [N- [1 ′]. , 3′-dimethylpyrazolyl] carboxyamino] ethyl-methacrylate and the like.

  The blocked isocyanato group and the blocked isothiocyanato group are, for example, a blocking agent having only one active hydrogen capable of reacting with an isocyanato group or an isothiocyanato group in one molecule of the blocking agent, and a compound having an isocyanato group or an isothiocyanato group. Can be produced by reacting.

  The blocking agent is preferably a compound that can be removed from these groups at a temperature of 170 ° C. or lower even after reacting with an isocyanato group and / 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, oxime compounds, amine compounds, imine compounds, and bisulfite. Examples thereof include salts, pyridine compounds, and pyrazole compounds. These blocking agents may be used alone or in combination of two or more. Examples of preferable blocking agents include oxime compounds and pyrazole compounds.

  The applicable blocking agent is specifically shown below. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like. Examples of the phenol compound include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester, and the like. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like. 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, γ-butyrolactam and the like. Examples of the acid imide compound include succinimide, maleic imide and the like. Examples of the imidazole compound include imidazole and 2-methylimidazole. Examples of urea compounds include urea, thiourea, ethyleneurea and the like. Examples of amine compounds include diphenylamine, aniline, carbazole and the like. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite include sodium bisulfite. Examples of pyridine compounds include 2-hydroxypyridine and 2-hydroxyquinoline. Examples of oxime compounds include formal oxime, acetal oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and the like. Examples of the pyrazole compound include 3,5-dimethylpyrazole, 3,5-diethylpyrazole and the like.

  The blocked isocyanato group and / or the blocked isothiocyanato group that the polymer compound (A) may have is preferably a group represented by the following formula (3) or a group represented by the following formula (4).

In the formulas (3) and (4), ^Xb represents an oxygen atom or a sulfur atom. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be different from each other and represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The definition, specific examples, and the like of the monovalent organic group having 1 to 20 carbon atoms that is R ^{8 to} R ¹² are as described above.

In one embodiment of the present invention, R ⁸ and R ⁹ in the formula (3) may be different from each other, and are preferably groups selected from the group consisting of a methyl group and an ethyl group. In another embodiment, R ¹⁰ and R ^{12 in} formula (4) are preferably methyl groups, and R ¹¹ is preferably a hydrogen atom.

  Examples of the blocked isocyanato group include O- (methylideneamino) carboxyamino group, O- (1-ethylideneamino) carboxyamino group, O- (1-methylethylideneamino) carboxyamino group, and O- [1-methylpropylene group. Ridenamino] carboxyamino group, (N-3,5-dimethylpyrazolylcarbonyl) amino group, (N-3-ethyl-5-methylpyrazolylcarbonyl) amino group, (N-3,5-diethylpyrazolylcarbonyl) amino group , (N-3-propyl-5-methylpyrazolylcarbonyl) amino group, (N-3-ethyl-5-propylpyrazolylcarbonyl) amino group, and the like.

  Examples of the blocked isothiocyanato group include O- (methylideneamino) thiocarboxyamino group, O- (1-ethylideneamino) thiocarboxyamino group, 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- Examples include diethylpyrazolylthiocarbonyl) amino group, (N-3-propyl-5-methylpyrazolylthiocarbonyl) amino group, and (N-3-ethyl-5-propylpyrazolylthiocarbonyl) amino group.

  As the at least one group (first functional group) selected from the group containing a blocked isocyanato group and a blocked isothiocyanato group according to the polymer compound (A) used in the present invention, a blocked isocyanato group is preferable. .

  In reacting a compound having an isocyanato group and / or an isothiocyanato group and an unsaturated bond in the molecule with a blocking agent, an organic solvent, a catalyst, or the like can be added and reacted as necessary.

  The charged molar ratio of the monomer having an unsaturated double bond and a blocked isocyanato group and / or a blocked isothiocyanato group in the molecule is preferably 1 mol% or more and 60 mol% or less with respect to all monomers involved in the polymerization. More preferably, they are 1 mol% or more and 30 mol% or less, More preferably, they are 1 mol% or more and 10 mol% or less. By adjusting the charge molar ratio of the monomer within this range, a crosslinked structure is sufficiently formed inside the cured product and the number of polar groups contained can be reduced. Therefore, when the polymer in which the monomer is polymerized is used for, for example, a gate insulating layer of an organic thin film transistor, polarization can be suppressed.

(At least one repeating unit selected from the group comprising a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group)
The polymer compound (A) includes at least one repeating unit selected from the group comprising a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group.

  In other words, the polymer compound (A) includes only a repeating unit having a hydroxy group, only a repeating unit having a carboxy group, or only a repeating unit having a hydroxy group and a carboxy group. In addition, a combination of two or more of a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group may be included.

  The polymer compound (A) contains at least one repeating unit selected from the group comprising a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group. Since it is easy, it is preferable that it is a repeating unit represented by following formula (2).

In said formula (2), R < ⁵ >, R < ⁶ >, R < ⁷ > may mutually differ and represents a hydrogen atom, a fluorine atom, or a C1-C20 monovalent organic group. R ^b is a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond of the group represented by the group represented by —NHCOO— is located on the carbon atom side to which R ⁵ in the formula (2) is bonded, the group in the formula (2) It may be located on the ^Xa side. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom. m2 represents the integer of 0-6. ^Xa represents a hydroxy group or a carboxy group.

In said formula (2), it is preferable that R < ⁵ >, R < ⁶ >, R < ⁷ > is a hydrogen atom or a methyl group. Moreover, it is preferable that m2 is an integer of 0-2.

Examples of the repeating unit represented by the formula (2) include a repeating unit represented by the following formula (2-1).

In the formula (2-1), R ⁵ , R ⁶ , R ⁷ and X ^a represent the same meaning as described above. Y ¹ represents a group represented by —COO—, a group represented by —NHCO—, a divalent organic group having 1 to 20 carbon atoms, or a direct bond. The bond on the carbon atom side of the group represented by —COO— is located on the carbon atom side to which R ⁵ in the formula (2-1) is bonded, and is represented by —NHCO—. The bond on the carbon atom side of the group is located on the carbon atom side to which R ⁵ in the formula (2-1) is bonded. When Y ¹ is a group represented by —COO— or a group represented by —NHCO—, Y ² represents a divalent organic group having 1 to 20 carbon atoms. When Y ¹ is a group represented by a divalent organic group having 1 to 20 carbon atoms, Y ² represents a direct bond. When Y ¹ is a direct bond, Y ² represents a direct bond.

  Examples of the monomer that is a raw material of the repeating unit having a hydroxy group and / or a carboxy group contained in the polymer compound (A) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy Butyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 4-hydroxymethylcyclohexyl acrylate, 2-hydroxy-1-methylethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, 2 -Hydroxyphenylethyl acrylate, 3-hydroxy-1-adamantyl acrylate, 2-hydroxycyclohexyl acrylate, 3-hydroxycyclohexyl acrylate Rate, 4-hydroxycyclohexyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, carboxymethyl acrylate, 2-carboxyethyl acrylate, 2-carboxypropyl acrylate, 3-carboxypropyl acrylate, 2-carboxybutyl acrylate, 4-carboxybutyl Acrylate, 6-carboxyhexyl acrylate, 8-carboxyoctyl acrylate, 4-carboxymethylcyclohexyl acrylate, 2-carboxy-1-methylethyl acrylate, 2-carboxyphenylethyl acrylate, 3-carboxy-1-adamantyl acrylate, 2-carboxy Cyclohexyl acrylate, 3-carboxycyclohexyl acrylate, 2-carboxy-3- Enoxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl methacrylate, 4- Hydroxymethylcyclohexyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, 2-hydroxyphenylethyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 2-hydroxycyclohexyl methacrylate, 3- Hydroxycyclohexyl methacrylate, 4-hydroxycyclohexyl methacrylate, 2 -Hydroxy-3-phenoxypropyl methacrylate, carboxymethyl methacrylate, 2-carboxyethyl methacrylate, 2-carboxypropyl methacrylate, 3-carboxypropyl methacrylate, 2-carboxybutyl methacrylate, 4-carboxybutyl methacrylate, 6-carboxyhexyl methacrylate, 8 -Carboxyoctyl methacrylate, 4-carboxymethylcyclohexyl methacrylate, 2-carboxy-1-methylethyl methacrylate, 2-carboxyphenylethyl methacrylate, 3-carboxy-1-adamantyl methacrylate, 2-carboxycyclohexyl methacrylate, 3-carboxycyclohexyl methacrylate, 2-carboxy-3-phenoxypropyl methacrylate Rate, 2-propen-1-ol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 2-allylphenol, 3-allyloxypropionic acid, allyl 4-hydroxybenzoate, ethylene glycol monoallyl ether, 3-allyloxy-1,2 -Propanediol, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid Acid, 2- (trifluoromethyl) acrylic acid, 6-acrylamidohexanoic acid, N- (2-hydroxyethyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, 2-acryloyloxyethyl-succinic acid, 2- Acryroy Xylethylhexahydrophthalic acid, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2,2-bis (allyloxymethyl) -1-butanol, 1,3 -Diallyloxy-2-propanol, 1,5-hexadiene-3,4-diol, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2- Hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate Chlorate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 3-perfluorooctyl- 2-hydroxypropyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- (perfluoro-5-methylhexyl) ) -2-hydroxypropyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 3-carboxy-2-hydroxypropyl acrylate and the like.

  The charge molar ratio of the monomer having an unsaturated double bond and a hydroxy group and / or a carboxy group in the molecule is preferably 1 mol% or more and 60 mol% or less, more preferably 1 mol% with respect to all monomers. It is from mol% to 30 mol%, more preferably from 1 mol% to 10 mol%.

  By adjusting the monomer charge molar ratio within this range, a sufficient crosslinked structure can be formed inside the gate insulating layer, and the number of polar groups contained can be reduced. As a result, the polarization of the gate insulating layer can be suppressed.

(Repeating unit represented by formula (1))
The polymer compound (A) includes a repeating unit represented by the following formula (1).

In said formula (1), R < ¹ >, R < ² >, R < ³ > may mutually differ and represents a hydrogen atom, a fluorine atom, or a C1-C20 monovalent organic group. R ⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group containing a fluorine atom. R ^a is represented by a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond represented by the group represented by the group represented by -NHCOO- is located on the carbon atom side to which R ¹ in the formula (1) is bonded, the group represented by the formula (1) It may be located on the carbon atom side constituting the benzene ring, and the hydrogen atom in the divalent organic group may be substituted with a fluorine atom. m1 represents the integer of 0-6. n1 represents the integer of 1-5.

When there are ^a plurality of R ^{a s} , they may be different from each other. When there are a plurality of R ⁴ , they may be different from each other. When there are a plurality of Rf, they may be different from each other.

  When the polymer compound (A) contains the repeating unit represented by the formula (1), the carrier mobility of the organic thin film transistor can be further improved.

In said formula (1), it is preferable that R < ¹ >, R < ² >, R < ³ > is a hydrogen atom or a methyl group mutually independently.

In the formula (1), R ^a is preferably ^a divalent organic group having 1 to 20 carbon atoms or a group represented by —COO—.

  In the formula (1), m1 is preferably an integer of 0 to 2.

  In the formula (1), n1 is preferably an integer of 1 to 5 because the hydrophobicity of the cured product obtained by curing the composition is improved.

  The content of the repeating unit represented by the formula (1) in the polymer compound (A) can increase the dielectric breakdown strength when a voltage is applied as a gate insulating layer, and is therefore 50% by mass or more. Preferably, it is 60 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more.

  Examples of the monomer as a raw material for the repeating unit represented by the formula (1) include 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, 2,3,4,5, 6-pentafluorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2-fluoro-α-methylstyrene, 3-fluoro-α-methylstyrene, 4-fluoro-α-methylstyrene, 4- Fluoro-β-methylstyrene, 4-trifluoromethyl-α-methylstyrene, 4-fluoro-2,6-dimethylstyrene, 2,3,4,5,6-pentafluorobenzyl acrylate, 2,3,4, 5,6-pentafluorobenzyl methacrylate, 2-fluorobenzyl acrylate, 2-fluorobenzyl methacrylate Rate, 3-fluorobenzyl acrylate, 3-fluorobenzyl methacrylate, 4-fluorobenzyl acrylate, 4-fluorobenzyl methacrylate, 4-trifluoromethylbenzyl acrylate, 4-trifluoromethylbenzyl methacrylate, 3- (4-fluorophenyl) -1-propene, 3-pentafluorophenyl-1-propene, 3- (4-trifluoromethylphenyl) -1-propene, (4-fluorophenyl) acrylate, (4-fluorophenyl) methacrylate, pentafluorophenyl acrylate , Pentafluorophenyl methacrylate, 2- (pentafluorophenyl) ethyl acrylate, 2- (pentafluorophenyl) ethyl methacrylate, 2- (4-fluorophenyl) ethyl Acrylate, 2- (4-fluorophenyl) ethyl methacrylate, N- (4-fluorophenyl) acrylamide, N- (4-fluorophenyl) methacrylamide, N- (pentafluorophenyl) acrylamide, N- (pentafluorophenyl) And methacrylamide.

(Monomers used as materials for other repeating units)
The polymer compound (A) includes a monomer having a blocked isocyanato group and / or a blocked isothiocyanato group, a monomer serving as a raw material of a repeating unit having a hydroxy group and / or a carboxy group, and a repeating represented by the above formula (1) You may add and manufacture the monomer used as the material of other repeating units other than the monomer used as the raw material of a unit.

  The amount of the monomer used as the material of the other repeating unit is usually when the amount of the monomer having an unsaturated double bond and a blocked isocyanato group and / or a blocked isothiocyanato group in the molecule is 100 mol%. 0 mol% or more and 90 mol% or less, 0 mol% or more and 80 mol% or less, and 0 mol% or more and 50 mol% or less.

  Examples of the “monomer serving as a material of another repeating unit” include 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. Derivatives, vinyl esters of organic carboxylic acids and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, dialkyl esters of fumaric acid and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, organic Examples thereof include N-vinylamide derivatives of carboxylic acids, maleimides and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and organic germanium derivatives.

  The “monomer serving as a material for other repeating units” is appropriately selected according to the characteristics required for the insulating layer. For example, when superior durability and small hysteresis are given priority, a monomer that forms a hard film with a high molecular density such as styrene or a styrene derivative can be selected. Since it is used as a gate insulating layer and improves adhesion to bonding surfaces such as the surface of a gate electrode and the surface of a substrate and can form a good interface, “a monomer as a material of another repeating unit” It is preferable to use a monomer capable of imparting flexibility such as an acid ester and a derivative thereof and an acrylic ester and a derivative thereof.

  Monofunctional acrylates and polyfunctional acrylates can be used as the acrylate esters and derivatives thereof, which are “monomers serving as materials for other repeating units”. Examples of acrylic 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, acrylic Hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1 , 4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane diacrylate, trimethylol proppant Acrylate, pentaerythritol pentaacrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoro Propyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3 -Methylbutyl) ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydride Xylpropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H Examples include -1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, and the like.

  Monofunctional methacrylates and polyfunctional methacrylates can be used as the methacrylic acid esters and derivatives thereof, which are “monomers serving as materials for other repeating units”. Methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid isobutyl, methacrylic acid-sec-butyl, methacrylic acid. Hexyl acid, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylo Rupropane trimethacrylate, pentaerythritol pentamethacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-acryloylmorpholine, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3 , 3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (Perfluoro-3-methylbutyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 1H, 1 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 and the like.

  Examples of styrene and its derivatives that are “monomers that are materials of other repeating units” include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 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-bromo Styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 2-vinyl bif Nyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-iso Propenyltoluene, 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, 4- (methoxymethoxy) styrene, 4- (methoxyethoxymethyloxy) styrene, 4- (1-ethoxyethyloxy) styrene, 2 -(Methoxymethoxycarbonyl) styrene 2- (methoxyethoxymethyloxycarbonyl) styrene, 2- (1-ethoxyethyloxycarbonyl) styrene, 2- (tetrahydropyranyloxycarbonyl) styrene, 3- (methoxymethoxycarbonyl) styrene, 3- (methoxyethoxymethyloxy) Carbonyl) styrene, 3- (1-ethoxyethyloxycarbonyl) styrene, 3- (tetrahydropyranyloxycarbonyl) styrene, 4- (methoxymethoxycarbonyl) styrene, 4- (methoxyethoxymethyloxycarbonyl) styrene, 4- ( 1-ethoxyethyloxycarbonyl) styrene, 4- (tetrahydropyranyloxycarbonyl) styrene and the like.

  Examples of acrylonitrile and its derivatives that are “monomers that are materials for other repeating units” include acrylonitrile and the like. Examples of methacrylonitrile and its derivatives include methacrylonitrile.

  Examples of vinyl esters of organic carboxylic acids and derivatives thereof that are “monomers that are materials for other repeating units” include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, and the like.

  Examples of allyl esters of organic carboxylic acids and derivatives thereof that are “monomers that are materials for other repeating units” include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate, etc. Is mentioned.

  Examples of the dialkyl ester of fumaric acid and its derivatives, which are “monomers as materials of other repeating units”, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, Examples include di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate, and the like.

  Examples of the dialkyl ester of maleic acid and its derivatives, which are “monomers that serve as materials for other repeating units”, include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, Examples include di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

  Examples of the dialkyl ester of itaconic acid which is a “monomer serving as a material of another repeating unit” and its derivatives include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, Examples include di-n-butyl itaconate, di-2-ethylhexyl itaconate, and dibenzyl itaconate.

  Examples of N-vinylamide derivatives of organic carboxylic acids that are “monomers that serve as materials for other repeating units” include N-methyl-N-vinylacetamide and the like.

  Examples of maleimide and its derivatives that are “monomers that are materials for other repeating units” include N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

  Examples of terminal unsaturated hydrocarbons and derivatives thereof that are “monomers that are materials for other repeating units” include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and the like. It is done.

  Examples of organic germanium derivatives that are “monomers that are materials of other repeating units” include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, triethylvinylgermanium, and the like.

  Of these “monomers that serve as materials for other repeating units”, alkyl acrylates, alkyl methacrylates, styrene, acrylonitrile, methacrylonitrile, and allyltrimethylgermanium are preferred.

<Composition>
The composition of this invention contains a high molecular compound (A).
The composition according to the present invention may contain two or more polymer compounds (A).

  Content of the high molecular compound (A) in a composition is 5 mass%-70 mass% normally with respect to the whole composition concerning this invention.

  In addition to the polymer compound (A), the composition according to the present invention does not include a repeating unit having a hydroxy group and / or a carboxy group, and has a repeating unit having a blocked isocyanato group and / or a blocked isothiocyanato group. One or more polymer compounds (B) containing may be contained.

  The content of the polymer compound (B) in the composition is usually 0 to 300 parts by weight when the content of the polymer compound (A) is 100 parts by weight.

  In addition to the polymer compound (A), the composition according to the present invention does not include a repeating unit containing a blocked isocyanato group or a blocked isothiocyanato group, and includes a repeating unit having a hydroxy group and / or a carboxy group. The polymer compound (C) containing 1 or more types may be included.

  The content of the polymer compound (C) in the composition is usually 0 to 300 parts by weight when the polymer compound (A) is 100 parts by weight.

The composition according to the present invention may contain a solvent for mixing and viscosity adjustment, an additive usually used in combination with a crosslinking agent when the polymer compound is crosslinked.
The content of additives and the like in the composition is usually 0 to 40 parts by weight when the polymer compound (A) is 100 parts by weight.

  Examples of the solvent used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatics such as xylene. Examples thereof include hydrocarbon solvents, ketone solvents such as acetone, acetate solvents such as butyl acetate, alcohol solvents such as isopropyl alcohol, halide solvents such as chloroform, and mixed solvents thereof. Moreover, as an additive, the catalyst for promoting a crosslinking reaction, a leveling agent, a viscosity modifier, etc. can be used.

  Since the composition concerning this invention can make the flatness of the surface of the hardened | cured film | membrane high, it is preferable to consist only of a high molecular compound (A) and an organic solvent.

<Use of polymer compound and composition>
The polymer compound of the present invention and the composition containing the polymer compound can be suitably used as a composition for an insulating layer of an organic thin film transistor.
A film obtained by curing the polymer compound of the present invention and a composition containing the polymer compound (composition for insulating layer) can be suitably used as a functional member of an organic thin film transistor.

  The film obtained by curing the composition of the present invention comprises, for example, a step of applying the composition of the present invention described above to the surface of a base material to be formed to form a coating layer, and a step of curing the coating layer. It can form by the manufacturing method containing.

  A method for producing a film obtained by curing the composition comprises preparing a coating solution for forming a film by adding a solvent (organic solvent) or the like to the composition of the present invention, if necessary, and based on the prepared coating solution. The film | membrane which hardened | cured the composition of this invention can be obtained by apply | coating to the surface of a material and hardening the formed coating layer.

  The organic solvent that can be used for preparing the coating solution is not particularly limited as long as it is an organic solvent that dissolves components such as a polymer compound and a crosslinking agent contained in the composition, and preferably has a boiling point at normal pressure. It is an organic solvent that is 100 ° C to 200 ° C. Examples of suitable organic solvents include 2-heptanone and propylene glycol monomethyl ether acetate. The coating solution for forming the film can contain a leveling agent, a surfactant, a curing catalyst, and the like as necessary.

  When using an organic solvent, the amount of the organic solvent contained in the coating solution is preferably 30% by mass to 95% by mass, and more preferably 60% by mass to 93% by mass with respect to the entire coating solution.

  The coating liquid for forming the film can be applied onto the substrate by a conventionally known coating method such as spin coating, die coating, screen printing, or ink jet.

  Specifically, a film obtained by curing the composition of the present invention can be suitably used as a gate insulating layer of an organic thin film transistor.

  If such a film is used particularly as a gate insulating layer of an organic thin film transistor, the carrier mobility of the organic thin film transistor can be effectively improved.

  The composition of the present invention (insulating layer composition) is excellent in insulation, sealing, adhesion, and solvent resistance when cured. Therefore, the composition of the present invention (insulating layer composition) can also be used as a material for protective layers such as overcoat layers and undercoat layers of organic thin film transistors.

  The organic thin film transistor of the present invention may include, for example, a film obtained by curing the composition of the present invention as an overcoat layer in addition to the gate insulating layer that is a film obtained by curing the composition of the present invention.

<Organic thin film transistor>
The organic thin film transistor of the present invention includes a gate insulating layer obtained by curing the composition of the present invention described above.
Hereinafter, an embodiment of an organic thin film transistor, which is a suitable application destination of the composition of the present invention, will be described with reference to the drawings.

  FIG. 1 is a schematic view schematically showing the structure of a bottom gate top contact type organic thin film transistor according to a first embodiment of the present invention.

  As shown in FIG. 1, the organic thin film transistor 10 of the first embodiment is formed on a substrate 1, a gate electrode 2 provided so as to be bonded to the main surface of the substrate 1, and a substrate 1 so as to cover the gate electrode 2. A gate insulating layer 3 provided, an organic semiconductor layer 4 which is bonded to the gate insulating layer 3 so as to cover the gate electrode 2; and an organic semiconductor layer 4 which is bonded to the organic semiconductor layer 4; A source electrode 5 and a drain electrode 6 that are provided so as to be spaced apart from each other so that the channel region overlaps the gate electrode 2 when viewed in the thickness direction of the substrate 1 (in plan view) with the region interposed therebetween, And an overcoat layer 7 provided so as to cover the gate electrode 2, the gate insulating layer 3, the organic semiconductor layer 4, the source electrode 5 and the drain electrode 6.

  FIG. 2 is a schematic diagram schematically showing the structure of a bottom gate bottom contact type organic thin film transistor 10 according to the second embodiment of the present invention.

  As shown in FIG. 2, the organic thin film transistor 10 of the second embodiment is formed on a substrate 1, a gate electrode 2 provided so as to be bonded to the main surface of the substrate 1, and a substrate 1 so as to cover the gate electrode 2. The provided gate insulating layer 3 is bonded to the gate insulating layer 3 so that the channel region overlaps the gate electrode 2 when viewed in the thickness direction of the substrate 1 with the channel region interposed therebetween (in plan view). A source electrode 5 and a drain electrode 6 provided apart from each other, a part of the source electrode 5 and the drain electrode 6 and a part of the gate insulating layer 3 including a channel region so as to straddle the source electrode 5 and the drain electrode 6. The organic semiconductor layer 4 provided to cover the gate electrode 2, the gate insulating layer 3, the organic semiconductor layer 4, the source electrode 5, and the drain electrode 6 provided on the substrate 1. It was and a overcoat layer 7.

  FIG. 3 is a schematic view schematically showing the structure of a top gate bottom contact type organic thin film transistor 10 according to the third embodiment of the present invention.

  As shown in FIG. 3, the organic thin film transistor 10 of the third embodiment includes a substrate 1, a source electrode 5 and a drain electrode 6 provided on the main surface of the substrate 1 so as to be separated from each other with a channel region interposed therebetween, The substrate 1 provided with the source electrode 5 and the drain electrode 6 is covered with the organic semiconductor layer 4 provided so as to straddle the source electrode 5 and the drain electrode 6, and the organic semiconductor layer 4, the source electrode 5, and the drain electrode 6. A gate insulating layer 3 provided on the gate insulating layer 3, a gate electrode 2 provided on the channel region so as to extend over the channel region, a source electrode 5, a drain electrode 6 provided on the substrate 1, and an organic semiconductor An overcoat layer 7 covering the layer 4, the gate insulating layer 3, and the gate electrode 2.

<Method for producing organic thin film transistor>
The bottom gate top contact type organic thin film transistor 10 of the first embodiment includes, for example, a substrate 1 (base) in which a gate electrode 2 is formed on the main surface of the substrate 1 and the gate electrode 2 is provided so as to cover the gate electrode 2. A gate insulating layer 3 is formed on the surface of the material, an organic semiconductor layer 4 is formed on the gate insulating layer 3, a source electrode 5 and a drain electrode 6 are formed so as to be joined to the organic semiconductor layer 4. For example, it can be manufactured by forming the overcoat layer 7 so as to cover the gate electrode 2, the gate insulating layer 3, the organic semiconductor layer 4, the source electrode 5 and the drain electrode 6 provided on the substrate 1.

  The bottom gate bottom contact type organic thin film transistor 10 of the second embodiment includes, for example, a substrate 1 (base) in which a gate electrode 2 is formed on the main surface of the substrate 1 and the gate electrode 2 is provided so as to cover the gate electrode 2. The gate insulating layer 3 is formed on the surface of the material, the source electrode 5 and the drain electrode 6 are formed on the gate insulating layer 3, and the source electrode 5 and the drain electrode 6 are straddled over the source electrode 5 and the drain electrode 6. The organic semiconductor layer 4 is formed so as to cover a part of the gate insulating layer 3 including the channel region, and if necessary, the gate electrode 2 provided on the substrate 1, the gate insulating layer 3, the organic semiconductor layer 4, It can be manufactured by forming the overcoat layer 7 so as to cover the source electrode 5 and the drain electrode 6.

  The top gate bottom contact type organic thin film transistor 10 according to the third embodiment includes, for example, an organic semiconductor in which the source electrode 5 and the drain electrode 6 are formed on the main surface of the substrate 1 and straddle the source electrode 5 and the drain electrode 6. The layer 4 is formed, the organic semiconductor layer 4, the source electrode 5 and the drain electrode 6 are formed, the gate insulating layer 3 is formed so as to cover the source electrode 5 and the drain electrode 6, and the gate is formed so as to straddle the channel region. It can be manufactured by forming the gate electrode 2 on the insulating layer 3 and, if necessary, forming the overcoat layer 7 so as to cover the gate insulating layer 3 and the gate electrode 2.

  The method for producing the organic thin film transistor 10 of the present invention (the step of forming the gate insulating layer 3) is the same as the “film obtained by curing the composition” already described, and a step of coating the surface of the substrate to form a coating layer. And a step of curing the coating layer.

  The drying step of the coating layer in the formation process of the gate insulating layer 3 aims at removing the solvent in the coating layer formed on the base material by the coating method. The purpose of the curing step is to form the gate insulating layer 3 in which the composition for the insulating layer is cured by causing a crosslinking reaction by the reactive functional group of the polymer compound in the coating layer to proceed.

  In the curing step of the composition for an insulating layer of the present invention, as a first step, the protecting group derived from the blocking agent is removed from the blocked isocyanato group and / or the blocked isothiocyanate group, and reacts with active hydrogen. Forming a possible isocyanato group and / or isothiocyanato group, and then, as a second step, the generated isocyanato group and / or isothiocyanato group includes a step of reacting with a hydroxy group and / or carboxy group containing active hydrogen. .

  Comparing the first stage and the second stage, the reaction of the first stage is slower than the reaction of the second stage. Thus, once the first stage is advanced, the second stage automatically proceeds. Therefore, in order to cure the composition for an insulating layer of the present invention, the first step may be advanced.

  In order to advance the first step, for example, electromagnetic waves or heat is applied to the coating layer. Specifically, applying electromagnetic waves or heat to the coating layer includes irradiating the coating layer with electromagnetic waves or firing the coating layer.

Irradiation of electromagnetic waves can be performed using, for example, an exposure apparatus conventionally used for manufacturing a semiconductor device or a UV lamp used for curing a UV curable resin.
Firing can be performed, for example, by heat treatment at a temperature of 80 ° C. to 300 ° C., preferably 120 ° C. to 250 ° C. for 5 minutes to 2 hours, preferably about 10 minutes to 1 hour. The irradiation conditions and firing conditions of electromagnetic waves for removing the protecting group derived from the blocking agent from the blocked isocyanato group and / or blocked isothiocyanato group are the type and amount of the blocked isocyanato group and / or blocked isothiocyanato group. It can be appropriately determined according to the above.

  The contact angle of the gate insulating layer 3 with respect to pure water is determined on the surface of the gate insulating layer 3 in consideration of the amount of fluorine atoms, hydrophobic functional groups and hydrophilic functional groups of the polymer compound in the insulating layer composition. It can be appropriately adjusted by increasing or decreasing the hydrophilicity.

  The hydrophilicity of the surface of the gate insulating layer 3 can be increased or decreased by adjusting the components of the atmosphere in which the heat treatment is performed. For example, if the drying step and the curing step (heating or baking) performed when forming the gate insulating layer 3 are performed in an atmosphere containing oxygen, the hydrophilicity of the surface of the gate insulating layer 3 increases, and the inert gas When performed in an atmosphere, the hydrophilicity of the surface of the gate insulating layer 3 is lowered. When heating is performed in an atmosphere containing oxygen, the hydrophilicity of the surface of the gate insulating layer 3 is further increased by increasing the temperature.

  In particular, by adjusting the amount of fluorine atoms, the surface energy of the gate insulating layer 3 can be adjusted to an appropriate range, and as a result, the interface with the organic semiconductor layer 4 can be a good interface. Thereby, the carrier mobility of an organic thin-film transistor can be improved more.

  By making the amount of fluorine atoms contained 1% by mass or more, the hysteresis characteristics of the organic thin film transistor can be sufficiently lowered, and by making it 60% by mass or less, the affinity with the organic semiconductor layer is kept good. A good interface can be formed when the organic semiconductor layer and the gate insulating layer are bonded.

  A self-assembled monolayer may be formed on the surface of the gate insulating layer 3 on the organic semiconductor layer 4 side. This self-assembled monolayer can be formed, for example, by treating the gate insulating layer 3 with a solution obtained by dissolving 1 to 10% by mass of an alkylchlorosilane compound or an alkylalkoxysilane compound in an organic solvent.

  Examples of the alkylchlorosilane compound for forming a self-assembled monolayer include methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, decyltrichlorosilane, octadecyltrichlorosilane, and the like.

  Examples of the alkylalkoxysilane compound for forming the self-assembled monolayer include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane and the like.

  The substrate 1, the gate electrode 2, the source electrode 5, the drain electrode 6, and the organic semiconductor layer 4 can be composed of materials and methods that are usually used in conventionally known methods for manufacturing organic thin film transistors. For example, as the substrate 1, a resin substrate or resin film, a plastic substrate or plastic film, a glass substrate, a silicon substrate, or the like is used. Examples of the material of the gate electrode 2, the source electrode 5, and the drain electrode 6 include chrome, gold, silver, and aluminum. The gate electrode 2, the source electrode 5, and the drain electrode 6 can be formed by a known method such as a coating method such as an evaporation method, a sputtering method, or an ink jet printing method.

  As an organic semiconductor compound that is a material of the organic semiconductor layer 4, π-conjugated polymers are widely used. For example, polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles, poly ( p-phenylene vinylene) and the like can be used.

  Moreover, as an organic-semiconductor compound which is a material of the organic-semiconductor layer 4, the low molecular compound which has the solubility to an organic solvent can be used. Examples of such low molecular weight compounds include polycyclic aromatic derivatives such as pentacene, phthalocyanine derivatives, perylene derivatives, tetrathiafulvalene derivatives, tetracyanoquinodimethane derivatives, fullerenes, carbon nanotubes, and the like. Specific examples of such low-molecular compounds include 9,9-di-n-octylfluorene-2,7-di (ethylene boronate) and 5,5′-dibromo-2,2′-. Examples include condensates with bithiophene.

  In the step of forming the organic semiconductor layer 4, for example, if necessary for the organic semiconductor compound, a solvent or the like is added to prepare a coating solution for forming the organic semiconductor layer 4. The coating is performed on the electrode 6 and the coating layer is dried. In the present invention, the polymer compound constituting the gate insulating layer 3 has a phenyl moiety or a carbonyl moiety, and has an affinity for an organic semiconductor compound. Therefore, a uniform and flat interface can be formed between the organic semiconductor layer 4 and the gate insulating layer 3 by the coating step and the drying step.

  The solvent that can be used in the step of forming the organic semiconductor layer 4 is not particularly limited as long as it is a solvent that can dissolve or disperse the organic semiconductor compound. As such a solvent, a solvent having a boiling point of 50 ° C. to 200 ° C. at normal pressure is preferable. Examples of such solvents include chloroform, toluene, anisole, 2-heptanone, propylene glycol monomethyl ether acetate and the like. The coating solution for forming the organic semiconductor layer 4 is gated by a known spin coating method, die coating method, screen printing method, ink jet printing method, or the like, as with the coating solution for forming the insulating layer 3 already described. It can be applied on the insulating layer 3.

  The overcoat layer 7 (protective layer) can be formed using the composition of the present invention already described, for example, in the same manner as in the step of forming the gate insulating layer 3 already described.

  Also, an undercoat layer (not shown) can be formed in the same manner as the overcoat layer 7.

  If the composition of this invention is used, the number of the components contained in a composition can be reduced. As a result, the process for forming the gate insulating layer, and thus the method for producing the organic thin film transistor can be more easily carried out.

<Uses of organic thin-film transistors>
A display member including an organic thin film transistor can be produced using the organic thin film transistor produced using the composition of the present invention. Moreover, the display provided with the member for a display can be manufactured using the member for a display containing this organic thin-film transistor.

  The organic thin film transistor formed using the composition of the present invention can also be used for an OFET sensor. The OFET sensor is a sensor that uses an organic thin film transistor (organic field effect transistor: OFET) as a signal conversion element that converts an input signal into an electric signal and outputs the signal, and has an electrode, an insulating layer, or an organic semiconductor layer. In addition, a sensitive function or a selective function is added. Examples of OFET sensors include biosensors, gas sensors, ion sensors, and humidity sensors.

  For example, the biosensor includes an organic thin film transistor having the configuration as described above. The organic thin film transistor has a probe (sensitive region) that specifically interacts with a target substance in a channel region and / or a gate insulating layer. When the concentration of the target substance is changed, the electrical characteristics of the probe are changed, so that it can function as a biosensor.

  As a method for detecting a target substance in a test sample, for example, biomolecules such as nucleic acids and proteins, or artificially synthesized functional groups are immobilized on the surface of a solid phase carrier, and these are used as probes. Is mentioned.

  In this method, specific affinity between substances or functional groups such as interaction of nucleic acid chains having complementary sequences, antigen-antibody reaction, enzyme-substrate reaction, receptor-ligand interaction, etc. is used. Then, the target substance is captured with the probe of the solid phase carrier. Therefore, a substance or functional group having specific affinity for the target substance is selected as the probe.

  The probe is immobilized on the surface of the solid phase carrier by a method corresponding to the type of the selected probe and the type of the solid phase carrier. Alternatively, a probe can be synthesized on the surface of a solid phase carrier (for example, a probe is synthesized by a nucleic acid extension reaction). In either case, a probe-target substance complex is formed on the surface of the solid phase carrier by bringing the probe immobilized on the surface of the solid phase carrier into contact with the test sample and treating the sample under appropriate conditions. . The channel region of the organic thin film transistor and / or the gate insulating layer itself may function as a probe.

  The gas sensor includes an organic thin film transistor having a configuration as described above. In the organic thin film transistor in this case, the channel region and / or the gate insulating layer functions as a gas sensitive part. When the gas to be detected comes into contact with the gas sensitive part, a change occurs in the electrical characteristics (conductivity, dielectric constant, etc.) of the gas sensitive part, so that it can function as a gas sensor.

Examples of the gas to be detected include an electron accepting gas and an electron donating gas. Examples of the electron-accepting gas include halogen acids such as F ₂ and Cl ₂ , organic acid gases such as nitrogen oxide gas, sulfur oxide gas, and acetic acid. Examples of the electron donating gas include amine gases such as ammonia gas and aniline, carbon monoxide gas, and hydrogen gas.

  The organic thin film transistor formed using the composition of the present invention can also be used for the production of a pressure sensor. The pressure sensor includes an organic thin film transistor having a configuration as described above. In this case, in the organic thin film transistor, the channel region and / or the gate insulating layer functions as a pressure sensitive part. When stress is applied to the pressure-sensitive part, the electrical characteristics of the pressure-sensitive part change, so that it can function as a pressure sensor.

  When the channel region functions as a pressure sensitive part, the organic thin film transistor may further include an alignment layer in order to further increase the crystallinity of the organic semiconductor contained in the channel region. Examples of the alignment layer include a monomolecular layer provided so as to be bonded to the gate insulating layer using a silane coupling agent such as hexamethyldisilazane.

  Moreover, the organic thin-film transistor formed using the composition of this invention can also be used for manufacture of a conductivity modulation type sensor. The conductivity modulation type sensor of the present invention uses a conductivity measuring element as a signal conversion element that converts an input signal into an electric signal and outputs it, and a film containing the composition of the present invention or the present invention. The film containing the composition is provided with a sensitivity function or a selectivity function with respect to an input to be detected. The conductivity modulation type sensor detects an input to be detected as a change in conductivity of the composition of the present invention. Examples of the conductivity modulation type sensor include a biosensor, a gas sensor, an ion sensor, and a humidity sensor.

  An organic thin film transistor formed using the composition of the present invention is an amplification circuit including an organic thin film transistor for amplifying output signals from various sensors such as a biosensor, a gas sensor, an ion sensor, a humidity sensor, and a pressure sensor. It can also be used for the manufacture of

  Moreover, the organic thin-film transistor formed using the composition of the present invention can also be used for manufacturing a sensor array in which a plurality of various sensors such as a biosensor, a gas sensor, an ion sensor, a humidity sensor, and a pressure sensor are integrated.

  In addition, the organic thin film transistor formed using the composition of the present invention integrates a plurality of various sensors such as biosensors, gas sensors, ion sensors, humidity sensors, and pressure sensors, and amplifies output signals from each sensor individually. Therefore, it can be used for manufacturing a sensor array with an amplifier circuit including an organic thin film transistor.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the examples described below.

(Molecular weight analysis)
The number average molecular weight and the weight average molecular weight of the polymer compound C described later were determined using gel permeation chromatography (GPC, manufactured by Waters, trade name: Alliance GPC 2000). The polymer compound C to be measured was dissolved in orthodichlorobenzene and injected into GPC. Orthodichlorobenzene was used for the mobile phase of GPC. The column used was “TSKgel GMHHR-H (S) HT (two linked, manufactured by Tosoh Corporation)”. A UV detector was used as the detector.

  The number average molecular weight and the weight average molecular weight of the polymer compounds 1 to 13 were determined using gel permeation chromatography (GPC, manufactured by Tosoh Corporation). THF was used for the mobile phase of GPC. As the column, “PLgel 10 μm MIXED-B (one, manufactured by Agilent Technologies)” was used. A UV detector was used as the detector.

Synthesis Example 1 (Synthesis of polymer compound C)
Polymer compound C was synthesized according to the following scheme.
After substituting the gas in reaction container with nitrogen gas, compound B-1 (286.8 mg, 0.200 mmol) represented by the following formula B-1 and compound B-2 represented by the following formula B-2 ( (77.6 mg, 0.200 mmol), 19 mL of tetrahydrofuran, 7.3 mg of tris (dibenzylideneacetone) dipalladium, and 9.3 mg of tri-tert-butylphosphonium tetrafluoroborate were added and stirred. 1.0 mL of 3 mol / L potassium phosphate aqueous solution was dripped at the obtained reaction solution, and it was made to recirculate | reflux for 3 hours. To the obtained reaction solution, 24.4 mg of phenylboronic acid was added and refluxed for 1 hour. To the resulting reaction solution, 0.1 g of sodium N, N-diethyldithiocarbamate trihydrate was added and refluxed for 3 hours. The obtained reaction solution was poured into water, toluene was added, and the toluene layer (toluene solution) was extracted. The obtained toluene solution was washed with an acetic acid aqueous solution and water, and then purified using a silica gel column. When the obtained toluene solution was dropped into acetone, a precipitate was obtained. The obtained precipitate was Soxhlet washed using acetone as a solvent to obtain a polymer compound C containing a repeating unit represented by the following formula. The yield of the high molecular compound C was 244 mg, the number average molecular weight of polystyrene conversion was 3.1 * 10 < ⁴ >, and the weight average molecular weight was 6.5 * 10 < ⁴ >.

Synthesis Example 2 (Synthesis of polymer compound (1))
Styrene (made by Junsei Kagaku) 3.22 g, 2,3,4,5,6-pentafluorostyrene (made by Aldrich) 3.61 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] 1.50 g of ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”), 0.71 g of 4-hydroxybutyl acrylate (made by Nippon Kasei Co., Ltd.), 2,2′-azobis (2-methylpropionitrile) ) 0.05 g, 6.05 g of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and oil at 60 ° C. Polymerized in a bath for 17 hours, the repeating unit represented by the following formula (i), the repeating unit represented by the following formula (ii), Repeating unit represented by the formula (iii), to give a viscous PGMEA solution polymer comprising repeating units represented by the following formula (iv) (1) is dissolved. The obtained polymer compound (1) had a polystyrene equivalent number average molecular weight of 1.2 × 10 ⁵ and a weight average molecular weight of 3.3 × 10 ⁵ .

Synthesis Example 3 (Synthesis of polymer compound (2))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 5.32 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl methacrylate (Showa Denko) Manufactured, trade name “Karenz MOI-BM”) 0.61 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.36 g, 2,2′-azobis (2-methylpropionitrile) 0.04 g, PGMEA ( 8.21 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 17 hours to obtain the following formula (v) A polymer unit comprising a repeating unit represented by the following formula (iii), a repeating unit represented by the following formula (iv) (2) There was obtained a viscous PGMEA solution dissolved. The obtained polymer compound (2) had a polystyrene equivalent number average molecular weight of 5.4 × 10 ⁴ and a weight average molecular weight of 4.5 × 10 ⁵ .

Synthesis Example 4 (Synthesis of polymer compound (3))
Styrene (manufactured by Junsei Kagaku) 3.13 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 3.50 g, 2- [O- [1'-methylpropylideneamino] carboxyamino] 1.45 g of ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”), 0.78 g of 2-hydroxyethyl methacrylate (made by Tokyo Chemical Industry Co., Ltd.), 2,2′-azobis (2-methylpropionitrile) ) 0.045g, 5.93g of PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) are put in a 50mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C for 16 hours. The repeating unit represented by the following formula (i), the repeating unit represented by the following formula (ii), the repeating unit represented by the following formula (iii), the following formula (v A polymer compound containing a repeating unit represented by) (3) to obtain a viscous PGMEA solution dissolved. The number average molecular weight of polystyrene conversion of the obtained polymer compound (3) was 9.2 × 10 ⁴ , and the weight average molecular weight was 2.2 × 10 ⁵ .

Synthesis Example 5 (Synthesis of polymer compound (4))
Styrene (manufactured by Junsei Kagaku) 3.18 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 3.55 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] 1.48 g of ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”), 0.53 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,2′-azobis (2-methylpropionitrile) 053 g, 5.85 g of PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) were put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C. for 16 hours. A repeating unit represented by the formula (i), a repeating unit represented by the following formula (ii), a repeating unit represented by the following formula (iii), and a repeating represented by the following formula (vii) Polymer compounds comprising units (4) to obtain a viscous PGMEA solution dissolved. The number average molecular weight in terms of polystyrene of the polymer compound (4) was 3.0 × 10 ⁴ , and the weight average molecular weight was 9.3 × 10 ⁴ .

Synthesis Example 6 (Synthesis of polymer compound (5))
Styrene (made by Junsei Kagaku) 3.02, g, 2,3,4,5,6-pentafluorostyrene (made by Aldrich) 3.38 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] 1.41 g of ethyl methacrylate (trade name “Karenz MOI-BM” manufactured by Showa Denko KK), 0.86 g of 4-vinylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,2′-azobis (2-methylpropionitrile) ) 0.043g, PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.80g are put into a 50mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in a 60 ° C oil bath for 16 hours. The repeating unit represented by the following formula (i), the repeating unit represented by the following formula (ii), the repeating unit represented by the following formula (iii), and the following formula (viii) Polymer compound containing a repeating unit (5) was obtained a viscous PGMEA solution dissolved. The number average molecular weight in terms of polystyrene of the polymer compound (5) was 4.1 × 10 ⁴ , and the weight average molecular weight was 1.3 × 10 ⁵ .

Synthesis Example 7 (Synthesis of polymer compound (6))
Styrene (made by Junsei Kagaku) 49.40 g, 2,3,4,5,6-pentafluorostyrene (made by Aldrich) 46.10 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] Ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”) 19.00 g, 2,2′-azobis (2-methylpropionitrile) 0.57 g, PGMEA (made by Wako Pure Chemical Industries) 76. 71 g was put into a 250 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, polymerized in an oil bath at 60 ° C. for 18 hours, and a repeating unit represented by the following formula (i): A viscous PGMEA solution in which the repeating unit represented by the following formula (ii) and the polymer compound (6) containing the repeating unit represented by the following formula (iii) were dissolved was obtained.

Synthesis Example 8 (Synthesis of polymer compound (7))
4-aminostyrene (manufactured by Aldrich) 18.60 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 70.79 g, 2,2′-azobis (2-methylpropionitrile) 45 g, PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) 134.75 g was put in a 250 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C. for 18 hours. A viscous PGMEA solution in which the polymer unit (7) containing the repeating unit represented by the formula (ii) and the repeating unit represented by the following formula (ix) was dissolved was obtained.

Synthesis Example 9 (Synthesis of polymer compound (8))
Styrene (made by Junsei Kagaku) 7.80 g, 2,3,4,5,6-pentafluorostyrene (made by Aldrich) 7.28 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] Ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”) 3.00 g, 2,2′-azobis (2-methylpropionitrile) 0.90 g, 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 12 .11 g was put into a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, polymerized in an oil bath at 60 ° C. for 18 hours, and the repeating unit represented by the following formula (i) A viscous 2-heptanone solution in which the polymer compound (8) containing a repeating unit represented by the following formula (ii) and a repeating unit represented by the following formula (iii) was dissolved was obtained. The number average molecular weight in terms of polystyrene of the polymer compound (8) was 7.7 × 10 ⁴ , and the weight average molecular weight was 1.4 × 10 ⁵ .

Synthesis Example 10 (Synthesis of polymer compound (9))
2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 3.57 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.90 g, 2,2′-azobis (2-methylpropionitrile) ) Put 0.022 g, 10.5 g of 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) into a 50 mL pressure vessel (manufactured by ACE GLASS), bubble with nitrogen gas, seal tightly, and in a 60 ° C. oil bath for 18 hours Polymerization was performed to obtain a viscous 2-heptanone solution in which the polymer unit (9) containing the repeating unit represented by the following formula (ii) and the repeating unit represented by the following formula (iv) was dissolved. . The number average molecular weight in terms of polystyrene of the polymer compound (9) was 4.2 × 10 ⁴ , and the weight average molecular weight was 7.6 × 10 ⁴ .

Synthesis Example 11 (Synthesis of polymer compound (10))
Styrene (manufactured by Junsei Kagaku) 2.87 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 3.20 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] Ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”) 1.33 g, 4-aminostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.66 g, 2,2′-azobis (2-methylpropionitrile) 0.040 g and 8.10 g of PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) are put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C. for 17 hours. , A repeating unit represented by the following formula (i), a repeating unit represented by the following formula (ii), a repeating unit represented by the following formula (iii), and a repeating unit represented by the following formula (ix) Polymer compounds comprising units returns (10) to precipitate as a gel.

Synthesis Example 12 (Synthesis of polymer compound (11))
4.19 g of styrene (manufactured by Junsei Kagaku), 3.94 g of 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich), 2- [O- [1′-methylpropylideneamino] carboxyamino] 0.81 g of ethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI-BM”), 0.48 g of 4-hydroxybutyl acrylate (made by Nippon Kasei Co., Ltd.), 2,2′-azobis (2-methylpropionitrile) ) 0.047 g, 6.29 g of PGMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) are put into a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C. for 17 hours. The repeating unit represented by the following formula (i), the repeating unit represented by the following formula (ii), the repeating unit represented by the following formula (iii), the following formula (iv) A polymer compound containing a repeating unit represented in (11) was obtained a viscous PGMEA solution dissolved. The number average molecular weight in terms of polystyrene of the polymer compound (11) was 6.9 × 10 ⁴ , and the weight average molecular weight was 1.7 × 10 ⁵ .

Synthesis Example 13 (Synthesis of polymer compound (12))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 3.62 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate (Showa Denko) Manufactured, trade name “Karenz MOI-BM”) 0.276 g, 4-hydroxybutyl acrylate (Nihon Kasei Co., Ltd.) 0.328 g, 2,2′-azobis (2-methylpropionitrile) 0.021 g, PGMEA ( 9.90 g (manufactured by Tokyo Chemical Industry Co., Ltd.) is placed in a 50 mL pressure vessel (ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 16 hours to obtain the following formula (v) A polymer compound comprising a repeating unit represented by the following formula, a repeating unit represented by the following formula (iii), and a repeating unit represented by the following formula (iv) (12) was obtained a viscous PGMEA solution dissolved. The number average molecular weight of polystyrene conversion of the obtained polymer compound (12) was 4.0 × 10 ⁴ , and the weight average molecular weight was 1.7 × 10 ⁵ .

Synthesis Example 14 (Synthesis of polymer compound (13))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 3.85 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl methacrylate (Showa Denko) Manufactured, trade name “Karenz MOI-BM”) 0.412 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.123 g, 2,2′-azobis (2-methylpropionitrile) 0.022 g, PGMEA ( 10.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) is put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 16 hours to obtain the following formula (v) A polymer compound comprising a repeating unit represented by the following formula, a repeating unit represented by the following formula (iii), and a repeating unit represented by the following formula (iv) (13) was obtained a viscous PGMEA solution dissolved. The obtained polymer compound (13) had a polystyrene-equivalent number average molecular weight of 3.9 × 10 ⁴ and a weight average molecular weight of 1.5 × 10 ⁵ .

Synthesis Example 15 (Synthesis of polymer compound (14))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 18.63 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl methacrylate (Showa Denko) Manufactured, trade name “Karenz MOI-BM”) 3.63 g, 4-vinylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.22 g, 2,2′-azobis (2-methylpropionitrile) 0.131 g, PGMEA ( 57.5 g (manufactured by Tokyo Chemical Industry Co., Ltd.) is put into a 125 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 16 hours to obtain the following formula (v) A polymer unit comprising a repeating unit represented by formula (iii): a repeating unit represented by formula (iii): a repeating unit represented by formula (viii): To give a viscous PGMEA solution dissolved. The obtained polymer compound (14) had a polystyrene-equivalent number average molecular weight of 3.9 × 10 ⁴ and a weight average molecular weight of 9.4 × 10 ⁴ .

Example 1 (Production and Evaluation of Organic Thin Film Transistor (1))
A uniform coating solution (1) was prepared by placing 15.14 g of the PGMEA solution of polymer compound (1) obtained in Synthesis Example 2 and 60.6 g of PGMEA in a 125 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor element (1) was manufactured using a solution containing the coating liquid (1) and the polymer compound A (sometimes referred to as an organic thin film transistor (1) or a transistor (1). The same). This will be specifically described below.

  A chromium (Cr) layer formed on the glass substrate by the photolithography process and the etching process was patterned to form a gate electrode.

  Subsequently, the coating liquid (1) is applied to the gate electrode side of the glass substrate on which the gate electrode is formed by spin coating, and the formed coating layer is heat-treated at 180 ° C. for 30 minutes, whereby the coating liquid (1). A gate insulating layer, which is a cured film obtained by curing the coating layer, was formed. The formed gate insulating layer had a thickness of 658 nm.

  Next, a source electrode and a drain electrode were formed by patterning a gold layer by a vapor deposition method on the gate insulating layer side of the glass substrate on which the gate insulating layer was formed.

  Next, the surfaces of the source electrode and the drain electrode formed on the glass substrate were modified by immersing the glass substrate on which the source electrode and the drain electrode were formed in a dilute solution of pentafluorobenzenethiol in isopropyl alcohol for 2 minutes. Subsequently, a toluene solution of 0.5% by mass of polymer compound C is spin-coated on the source electrode and drain electrode sides, and heat treatment is performed at 120 ° C. for 30 minutes using a hot plate to form an organic semiconductor layer. An organic thin film transistor (1) was obtained. The manufactured organic thin film transistor (1) had a channel length of 20 μm and a channel width of 2 mm.

  The obtained organic thin film transistor (1) was evaluated. Specifically, the transistor characteristics are obtained under the condition that a voltage is applied to the gate electrode of the organic thin film transistor (1) to change the gate voltage Vg from 20 V to -40 V and the source-drain voltage Vsd from 0 V to -40 V. Was measured using a vacuum probe (BCT22MDC-5-HT-SCU; Nagase Electronic Equipment Service Co., LTD). The results are shown in Table 1 below.

The carrier mobility of the organic thin film transistor (1) was 0.43 cm ² / Vs.

Example 2 (Production and Evaluation of Organic Thin Film Transistor (2))
A uniform coating solution (2) was prepared by placing 12.6 g of the PGMEA solution of the polymer compound (2) obtained in Synthesis Example 3 and 34.8 g of PGMEA in a 100 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (2) was produced in the same manner as in Example 1 except that the coating liquid (2) was used for forming the gate insulating layer, and the transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 657 nm. The carrier mobility of the obtained organic thin-film transistor (2) was 0.66 cm ² / Vs.

Example 3 (Production and Evaluation of Organic Thin Film Transistor (3))
A uniform coating solution (3) was prepared by putting 14.8 g of the PGMEA solution of the polymer compound (3) obtained in Synthesis Example 4 and 52.4 g of PGMEA into a 100 mL sample bottle, and dissolving by stirring.

  A bottom gate bottom contact type organic thin film transistor (3) was produced in the same manner as in Example 1 except that the coating liquid (3) was used for forming the gate insulating layer, and the transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 550 nm. The carrier mobility of the obtained organic thin-film transistor (3) was 0.44 cm ² / Vs.

Example 4 (Production and Evaluation of Organic Thin Film Transistor (4))
A uniform coating solution (4) was prepared by putting 14.6 g of PGMEA solution of polymer compound (4) obtained in Synthesis Example 5 and 51.2 g of PGMEA into a 100 mL sample bottle, and dissolving by stirring.

  A bottom gate bottom contact type organic thin film transistor (4) was produced in the same manner as in Example 1 except that the coating liquid (4) was used for forming the gate insulating layer, and transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The thickness of the formed gate insulating layer was 615 nm. The carrier mobility of the obtained organic thin film transistor (4) was 0.43 cm ² / Vs.

Example 5 (Production and Evaluation of Organic Thin Film Transistor (5))
A uniform coating solution (5) was prepared by placing 14.5 g of the PGMEA solution of the polymer compound (5) obtained in Synthesis Example 6 and 50.7 g of PGMEA in a 100 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (5) was produced in the same manner as in Example 1 except that the coating liquid (5) was used for forming the gate insulating layer, and transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The thickness of the formed gate insulating layer was 625 nm. The carrier mobility of the obtained organic thin-film transistor (5) was 0.43 cm ² / Vs.

Example 6 (Production and Evaluation of Organic Thin Film Transistor (6))
A uniform coating solution (6) was prepared by putting 15.7 g of the PGMEA solution of the polymer compound (11) obtained in Synthesis Example 12 and 55.1 g of PGMEA into a 100 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (6) was produced in the same manner as in Example 1 except that the coating liquid (6) was used for forming the gate insulating layer, and the transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 646 nm. The obtained organic thin film transistor (6) had a carrier mobility of 0.86 cm ² / Vs.

Example 7 (Production and Evaluation of Organic Thin Film Transistor (7))
A uniform coating solution (7) was prepared by putting 14.1 g of the PGMEA solution of the polymer compound (12) obtained in Synthesis Example 13 and 17.7 g of PGMEA into a 50 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (7) was produced in the same manner as in Example 1 except that the coating liquid (7) was used for forming the gate insulating layer, and transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 613 nm. The carrier mobility of the obtained organic thin-film transistor (7) was 0.45 cm ² / Vs.

Example 8 (Production and Evaluation of Organic Thin Film Transistor (8))
A uniform coating solution (8) was prepared by placing 14.6 g of the PGMEA solution of the polymer compound (13) obtained in Synthesis Example 14 and 18.2 g of PGMEA in a 50 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (8) was produced in the same manner as in Example 1 except that the coating liquid (8) was used for forming the gate insulating layer, and the transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 645 nm. The carrier mobility of the obtained organic thin film transistor (8) was 0.52 cm ² / Vs.

Example 9 (Production and Evaluation of Organic Thin Film Transistor (11))
A uniform coating solution (11) was prepared by putting 82.1 g of the PGMEA solution of the polymer compound (14) obtained in Synthesis Example 15 and 41.0 g of PGMEA into a 150 mL sample bottle and dissolving them by stirring.

  A bottom gate bottom contact type organic thin film transistor (11) was manufactured in the same manner as in Example 1 except that the coating liquid (11) was used for forming the gate insulating layer, and transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 1280 nm. The carrier mobility of the obtained organic thin film transistor (11) was 0.48 cm ² / Vs.

Comparative Example 1 (Production and Evaluation of Organic Thin Film Transistor (9))
10.00 g of the PGMEA solution of the polymer compound (6) obtained in Synthesis Example 7 and 5.93 g of the PGMEA solution of the polymer compound (7) obtained in Synthesis Example 8 and 55.82 g of PGMEA were placed in a 125 mL sample bottle and stirred. Then, a uniform coating solution (9) was prepared by dissolving. The number average molecular weight in terms of polystyrene of the polymer compound contained in the coating liquid (9) was 8.7 × 10 ⁴ , and the weight average molecular weight was 2.6 × 10 ⁵ .

  A bottom gate bottom contact type organic thin film transistor (9) was produced in the same manner as in Example 1 except that the coating liquid (9) was used for forming the gate insulating layer, and the transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The thickness of the formed gate insulating layer was 621 nm. The obtained organic thin film transistor (9) had a carrier mobility of 0.27 cm ² / Vs.

Comparative Example 2 (Production and Evaluation of Organic Thin Film Transistor (10))
100 mL of 18.09 g of 2-heptanone solution of polymer compound (8) obtained in Synthesis Example 9, 14.17 g of 2-heptanone solution of polymer compound (9) obtained in Synthesis Example 10, and 43.27 g of 2-heptanone The uniform coating liquid (10) was prepared by putting it into the sample bottle and stirring and dissolving. The number average molecular weight in terms of polystyrene of the polymer compound contained in the coating liquid (10) was 6.0 × 10 ⁴ , and the weight average molecular weight was 1.2 × 10 ⁵ .

  A bottom gate bottom contact type organic thin film transistor (10) was produced in the same manner as in Example 1 except that the coating liquid (10) was used for forming the gate insulating layer, and transistor characteristics were measured and evaluated. The results are shown in Table 1 below.

The formed gate insulating layer had a thickness of 675 nm. The obtained organic thin film transistor (10) had a carrier mobility of 0.28 cm ² / Vs.

  As is apparent from Table 1, according to Examples 1 to 9 of the present invention, carrier mobility is higher than that of Comparative Examples 1 and 2 in which a plurality of types of polymer compounds are mixed in forming the gate insulating layer. Could be higher.

Example 10 (Production and Evaluation of Organic Thin Film Transistor (12))
Using the coating liquid (7) obtained in Example 7, a top gate bottom contact type organic thin film transistor (12) was produced. This will be specifically described below.

  First, after irradiating ozone UV with respect to the glass substrate, it wash | cleaned with the alkali cleaning liquid and rinsed with the pure water.

  Next, a chromium layer and a gold layer were laminated in this order on the glass substrate from the substrate side by sputtering, and patterned by a photolithography process and an etching process, thereby forming a source electrode and a drain electrode. . The channel length of the source electrode and the drain electrode was 10 μm, and the channel width was 2 mm. Thereafter, the electrode formed on the glass substrate (particularly, by immersing the glass substrate in isopropyl alcohol diluted with 2,3,4,5,6-tetrafluoro-4- (trifluoromethyl) benzenethiol for 2 minutes) The surface of the gold layer) was modified.

  Subsequently, the toluene solution of 0.5% by mass of the polymer compound C obtained in Synthesis Example 1 is applied to the source electrode and drain electrode side by a spin coating method, and is heated at 150 ° C. for 7 minutes using a hot plate. Thus, an organic semiconductor layer was formed.

  On this organic semiconductor layer, a coating liquid (7) is applied by spin coating, and the formed coating layer is heat-treated at 150 ° C. for 30 minutes to form a cured film obtained by curing the coating layer. A layer was formed. The thickness of the formed gate insulating layer was 1040 nm.

  Furthermore, an organic thin film transistor (12) was obtained by forming an aluminum layer on the gate insulating layer by vapor deposition to form a gate electrode.

The obtained organic thin film transistor (12) was evaluated.
Specifically, using a vacuum probe (BCT22MDC-5-HT-SCU; manufactured by Nagase Electronic Equipment Service Co., LTD), a voltage is applied to the gate electrode of the organic thin film transistor (12) to obtain a gate voltage Vg. The carrier mobility was measured under the condition that the source-drain voltage Vsd was changed from 0 V to -40 V while the voltage was changed from 20 V to -40 V.

The carrier mobility of the organic thin film transistor (12) was 0.81 cm ² / Vs.
The results are shown in Table 2 below.

Example 11 (Production and Evaluation of Organic Thin Film Transistor (13))
A top gate / bottom contact type organic thin film transistor (13) was produced in the same manner as in Example 10 except that the coating liquid (11) obtained in Example 9 was used to form the gate insulating layer, and the transistor characteristics were measured. And evaluated. The results are shown in Table 2 below.

The formed gate insulating layer had a thickness of 926 nm. The obtained organic thin film transistor (13) had a carrier mobility of 0.86 cm ² / Vs.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Gate electrode 3 Gate insulating layer 4 Organic semiconductor layer 5 Source electrode 6 Drain electrode 7 Overcoat layer 10 Organic thin film transistor

Claims (10)

A repeating unit having at least one group selected from the group comprising a blocked isocyanato group and a blocked isothiocyanato group;
At least one repeating unit selected from the group comprising a repeating unit having a hydroxy group, a repeating unit having a carboxy group, and a repeating unit having a hydroxy group and a carboxy group;
The high molecular compound containing the repeating unit represented by following formula (1).

(In the formula (1),
R ¹ , R ² , and R ³ may be different from each other, and represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms.
R ⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or a monovalent organic group having 1 to 20 carbon atoms.
Rf represents a fluorine atom or a monovalent organic group containing a fluorine atom.
R ^a is represented by a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond represented by the group represented by the group represented by -NHCOO- is located on the carbon atom side to which R ¹ in the formula (1) is bonded, the group represented by the formula (1) It may be located on the carbon atom side constituting the benzene ring, and the hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
m1 represents the integer of 0-6.
n1 represents the integer of 1-5.
When there are ^a plurality of R ^{a s} , they may be different from each other. When there are a plurality of R ⁴ , they may be different from each other. When there are a plurality of Rf, they may be different from each other. ) The polymer compound according to claim 1, wherein the repeating unit having a hydroxy group and the repeating unit having a carboxy group are a repeating unit represented by the following formula (2).

(In the formula (2),
R ⁵ , R ⁶ , and R ⁷ may be different from each other, and represent a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms. R ^b is a divalent organic group having 1 to 20 carbon atoms, a group represented by —O—, a group represented by —CO—, a group represented by —COO—, or —NHCO—. Or a group represented by -NHCOO-, a group represented by -O-, a group represented by -CO-, a group represented by -COO-, or -NHCO- Even if the bond of the group represented by the group represented by —NHCOO— is located on the carbon atom side to which R ⁵ in the formula (2) is bonded, the group in the formula (2) It may be located on the ^Xa side. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
m2 represents the integer of 0-6.
^Xa represents a hydroxy group or a carboxy group. ) The polymer compound according to claim 1 or 2, wherein the blocked isocyanato group or blocked isothiocyanato group is a group represented by the following formula (3) or a group represented by the following formula (4).

(In the formulas (3) and (4),
^Xb represents an oxygen atom or a sulfur atom.
R ^{8 to} R ¹² may be different from each other and represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. )   The composition containing the high molecular compound as described in any one of Claims 1-3.   The composition of Claim 4 which consists only of the high molecular compound and organic solvent as described in any one of Claims 1-3.   The composition for insulating layers of the organic thin-film transistor which consists of a composition of Claim 4 or 5.   The film | membrane which hardened | cured the composition as described in any one of Claims 4-6.   An organic thin film transistor comprising the film according to claim 7 as a gate insulating layer.   The organic thin-film transistor of Claim 8 which further contains the film | membrane of Claim 7 as an overcoat layer. Applying the composition according to any one of claims 4 to 6 to a surface of a substrate to form a coating layer;
A method for producing an organic thin film transistor, comprising: curing the coating layer.

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