JP6405772B2 - Composition and organic thin film transistor using the same - Google Patents

Description

  The present invention relates to a composition and an organic thin film transistor using the composition.

  Since an organic thin film transistor using an organic semiconductor material can be manufactured at a lower temperature than a thin film transistor using a conventional inorganic semiconductor material, a flexible substrate typified by a plastic substrate can be used. In addition, since a high molecular compound is used as the organic semiconductor material, a film can be formed by a coating method typified by a spin coating method, an ink jet printing method, or a reverse printing method, and thus a simple manufacturing process is possible. For this reason, research and development of organic thin film transistors using organic semiconductor materials has been actively conducted.

A field effect organic thin film transistor which is a kind of organic thin film transistor has a gate electrode, a source electrode, a drain electrode, an organic semiconductor layer, and a gate insulating layer.
Since the organic semiconductor layer is located on the uppermost layer of the organic thin film transistor, the bottom gate type field effect organic thin film transistor usually has an overcoat layer (also called a protective layer) in order to block the organic semiconductor layer from the outside air. On the other hand, in a top gate type field effect organic thin film transistor, since the gate insulating layer is located on the uppermost layer of the organic thin film transistor, the gate insulating layer usually functions as an overcoat layer. These overcoat layers also have a function of protecting from a display device formed on the organic thin film transistor.
Since it is necessary to join the drain electrode of the organic thin film transistor and the electrode of the display device, these electrodes are joined by forming a via hole (also called a contact hole or a through hole) in the gate insulating layer or overcoat layer. Is done.

  A gate insulating layer and an overcoat layer of an organic thin film transistor are required to have flatness and adhesion to an adjacent layer, to have a low dielectric loss tangent and to have high insulation resistance. In addition, since the bottom gate type field effect organic thin film transistor forms an organic semiconductor layer on the gate insulating layer, when the organic semiconductor layer is formed by a coating method, the gate insulating layer needs to be cured by crosslinking. Is done.

  As a material used for a gate insulating layer of an organic thin film transistor, a composition containing an epoxy resin and a silane coupling agent is known (Patent Document 1). By curing the epoxy resin by crosslinking and protecting the hydroxyl group generated during curing with a silane coupling agent, a gate insulating layer having excellent durability in addition to the above characteristics can be obtained.

  Moreover, the composition containing polyvinylphenol and a melamine compound is known as a material used for the gate insulating layer of an organic thin-film transistor (nonpatent literature 1). Since the polyvinyl phenol and the melamine compound are cured by crosslinking, and the hydroxyl group of the polyvinyl phenol is removed during the curing, the gate insulating layer is excellent in durability in addition to the above characteristics.

JP2007-305950A

Appl. Phys. Lett. 89,093507 (2006)

  However, when the gate insulating layer or the overcoat layer is formed of the above material, there is a problem that the curing temperature is high.

  Accordingly, the present invention provides a composition having a low curing temperature, a method for producing a film using the composition, a film produced by the production method, and insulating the film when forming a gate insulating layer or an overcoat layer. An object is to provide an organic thin film transistor in a layer.

（１）
［式中、Ｒ^１は、水素原子又はメチル基を表す。ａは、０〜１０の整数を表し、ｎは、１〜５の整数を表す。Ｒ^ａは、アルキレン基、シクロアルキレン基、アリーレン基、−ＣＯ−で表される基、−ＣＯＯ−で表される基、−ＮＨＣＯ−で表される基、または、−ＮＨＣＯＯ−で表される基を表す。なお前記「−」で表される結合手は、左側の結合手が式（１）中の上側の結合手であってもよく、右側の結合手が式（１）中の上側の結合手であってもよい。これらのうち、アルキレン基、シクロアルキレン基およびアリーレン基が有する水素原子は、フッ素原子で置換されていてもよい。Ｒ^ａが複数ある場合、それらは同一でも異なっていてもよい。Ｒは、酸により脱離する１価の有機基を表す。Ｒが複数ある場合、それらは同一でも異なっていてもよい。 ］

（２）
［式中、Ｒ^２は、水素原子又はメチル基を表す。ｂは、０〜１０の整数を表し、ｍは、１〜５の整数を表す。Ｒ^ｂは、アルキレン基、シクロアルキレン基、アリーレン基、−ＣＯ−で表される基、−ＣＯＯ−で表される基、−ＮＨＣＯ−で表される基、または、−ＮＨＣＯＯ−で表される基を表す。なお前記「−」で表される結合手は、左側の結合手が式（２）中の上側の結合手であってもよく、右側の結合手が式（２）中の上側の結合手であってもよい。これらのうち、アルキレン基、シクロアルキレン基およびアリーレン基が有する水素原子は、フッ素原子で置換されていてもよい。Ｒ^ｂが複数ある場合、それらは同一でも異なっていてもよい。 Ｒ’’は、水素原子又は炭素数１〜２０の１価の有機基を表す。該炭素原子数１〜２０の１価の有機基はフッ素原子を有しない。Ｒ’’が複数個ある場合、それらは同一でも異なっていてもよい。Ｒｆは、フッ素原子又はフッ素原子を有する炭素数１〜２０の１価の有機基を表す。Ｒｆが複数個ある場合、それらは同一でも異なっていてもよい。］
［２］前記高分子化合物（Ａ）が、２５℃においてアルコール溶媒に５重量％未満しか溶解しない高分子化合物である、［１］に記載の組成物。
［３］前記化合物（Ｂ）が、スルホン酸エステル化合物、トリアジン化合物、スルホニウム塩、ヨードニウム塩またはブロック酸化合物である、［１］または［２］に記載の組成物。
［４］前記化合物（Ｃ）が、メラミン化合物またはユリア化合物である、［１］〜［３］のいずれかに記載の組成物。
［５］更に、下記式（３）で表される化合物（Ｄ）を含有する、［１］〜［４］のいずれかに記載の組成物。

（３）
［式中、Ｒ^１２は、水素原子又はメチル基を表す。Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。該炭素原子数１〜２０の１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。］
［６］さらに、溶媒を含有する、［１］〜［５］のいずれかに記載の組成物。
［７］［６］に記載の組成物を基材上に塗布することにより、膜を形成する工程と、
膜中に含有される前記高分子化合物（Ａ）の分子同士を架橋させる工程とを含む、膜の製造方法。
［８］［７］に記載の製造方法により製造された膜。
［９］［８］に記載の膜を、絶縁層に有する有機薄膜トランジスタ。
［１０］前記絶縁層が、ゲート絶縁層および／またはオーバーコート層である、［９］に記載の有機薄膜トランジスタ。
［１１］［９］または［１０］に記載の有機薄膜トランジスタを有する電子デバイス。 [1] A polymer compound (A) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and decomposed by irradiation with electromagnetic waves or electron beams, or by heating. A composition containing a compound (B) that generates an acid and a compound (C) that can react with two or more hydroxyl groups in the presence of an acid to form a cross-linked structure between molecules of the polymer compound (A). object.

(1)
[Wherein, R ¹ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 10, and n represents an integer of 1 to 5. R ^a is represented by an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or —NHCOO—. Represents a group. In the bond represented by “−”, the left hand may be the upper hand in Formula (1), and the right hand may be the upper hand in Formula (1). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. When there are a plurality of R ^{a s} , they may be the same or different. R represents a monovalent organic group that is eliminated by an acid. When there are a plurality of R, they may be the same or different. ]

(2)
[Wherein R ² represents a hydrogen atom or a methyl group. b represents an integer of 0 to 10, and m represents an integer of 1 to 5. R ^b is an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or a group represented by —NHCOO—. Represents a group. In the bond represented by “−”, the left hand may be the upper hand in Formula (2), and the right hand may be the upper hand in Formula (2). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. When there are a plurality of R ^{b s} , they may be the same or different. R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms does not have a fluorine atom. When there are a plurality of R ″, they may be the same or different. Rf represents a C1-C20 monovalent organic group which has a fluorine atom or a fluorine atom. When there are a plurality of Rf, they may be the same or different. ]
[2] The composition according to [1], wherein the polymer compound (A) is a polymer compound that dissolves less than 5% by weight in an alcohol solvent at 25 ° C.
[3] The composition according to [1] or [2], wherein the compound (B) is a sulfonic acid ester compound, a triazine compound, a sulfonium salt, an iodonium salt, or a block acid compound.
[4] The composition according to any one of [1] to [3], wherein the compound (C) is a melamine compound or a urea compound.
[5] The composition according to any one of [1] to [4], further comprising a compound (D) represented by the following formula (3).

(3)
[Wherein, R ¹² represents a hydrogen atom or a methyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ]
[6] The composition according to any one of [1] to [5], further comprising a solvent.
[7] A step of forming a film by applying the composition according to [6] on a substrate;
And a step of crosslinking the molecules of the polymer compound (A) contained in the membrane.
[8] A film produced by the production method according to [7].
[9] An organic thin film transistor having the film according to [8] as an insulating layer.
[10] The organic thin film transistor according to [9], wherein the insulating layer is a gate insulating layer and / or an overcoat layer.
[11] An electronic device having the organic thin film transistor according to [9] or [10].

  According to the present invention, a composition capable of forming a gate insulating layer or an overcoat layer at a low curing temperature can be provided. Furthermore, according to this invention, the composition which can form a gate insulating layer or an overcoat layer in a short hardening time can also be provided.

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

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

<Explanation of common terms>
Hereinafter, terms commonly used in the present specification have the following meanings unless otherwise specified.

“Polymer compound” means a compound having a molecular weight of 1000 or more. The polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or other embodiments.

The alkyl group may be a linear alkyl group or a branched alkyl group. The straight-chain alkyl group usually has 1 to 30 carbon atoms, and the branched alkyl group usually has 3 to 30 carbon atoms. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in the substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30. The number of carbon atoms in the cycloalkyl group does not include the number of carbon atoms in the substituent.
Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group and n-hexadecyl group, isopropyl Group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, etc. Groups. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
The alkyl group may have a substituent, and examples of the substituent include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom. The cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom. Examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The alkoxy group may be a linear alkoxy group or a branched alkoxy group. The straight-chain alkoxy group usually has 1 to 30 carbon atoms, and the branched alkoxy group usually has 3 to 30 carbon atoms. The number of carbon atoms of the alkoxy group does not include the number of carbon atoms of the substituent. The number of carbon atoms of the cycloalkoxy group is usually 3-30. The number of carbon atoms in the cycloalkoxy group does not include the number of carbon atoms in the substituent.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, and an n-hexadecyloxy group. Linear alkoxy group, isopropyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, 2-hexyldecyloxy group, 2-octyldodecyloxy group And branched alkoxy groups such as 2-decyltetradecyloxy group. Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.
The alkoxy group may have a substituent, and examples of the substituent include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom. The cycloalkoxy group may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom.

The aryl group is the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20. The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.
The aromatic hydrocarbon includes a compound in which two or more selected from the group consisting of benzene, a hydrocarbon condensed ring compound containing benzene, and a hydrocarbon condensed ring compound containing benzene and benzene are directly bonded.
As the aryl group, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Examples include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, and 4-phenylphenyl group.
The aryl group may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a monovalent heterocyclic group, and a halogen atom. An alkyl group or a cycloalkyl group Group is preferred, and an alkyl group is more preferred.

The monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from a heterocyclic compound. The number of carbon atoms of the heterocyclic compound is usually 2-30, preferably 3-20. The number of carbon atoms in the monovalent heterocyclic group does not include the number of carbon atoms in the substituent. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.
A heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. In the ring.
The heterocyclic compound is selected from the group consisting of a monocyclic heterocyclic compound, a condensed ring compound containing a heterocyclic compound, a monocyclic heterocyclic compound and a condensed ring compound containing a heterocyclic compound. The compounds in which the above are directly bonded are included.
The monovalent heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a halogen atom. An alkyl group or a cycloalkyl group Group is preferred, and an alkyl group is more preferred.
Examples of the monovalent heterocyclic group include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a 2-oxazolyl group, and a 2-thiazolyl group. 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group, 4- (2,1,3-benzothiadiazolyl) ) Group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkylene group may be a linear alkylene group or a branched alkylene group. The straight-chain alkylene group usually has 1 to 20 carbon atoms, and the branched alkylene group usually has 3 to 20 carbon atoms. The number of carbon atoms of the alkylene group does not include the number of carbon atoms of the substituent. The number of carbon atoms in the cycloalkylene group is usually 3-20. The number of carbon atoms in the cycloalkylene group does not include the number of carbon atoms in the substituent.
The alkylene group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a cyano group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an alkylcarbonyloxy group, a cyclo Examples thereof include an alkylcarbonyloxy group, an alkyloxycarbonyl group, and a cycloalkyloxycarbonyl group.
Examples of the alkylene 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. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

The arylene group is a remaining atomic group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon is usually 6-20. The number of carbon atoms of the arylene group does not include the number of carbon atoms of the substituent. The arylene group may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, and a halogen atom. Or a cycloalkyl group is preferable and an alkyl group is more preferable.
Examples of the arylene group include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, phenylenemethylene group, phenylenedimethylene group, phenylenetrimethylene group, phenylenetetramethylene group, methylnaphthylene group, dimethylnaphthylene group. Examples include a len group, a trimethyl naphthylene group, a vinyl naphthylene group, an ethenyl naphthylene group, a methyl anthrylene group, and an ethyl anthrylene group.

<Composition>
The composition of the present invention comprises a polymer compound (A), a compound (B) that generates an acid upon irradiation with electromagnetic waves or electron beams, or heating, and two or more hydroxyl groups in the presence of an acid. And a compound (C) capable of forming a cross-linked structure between molecules of the polymer compound (A) by reaction.

<Polymer Compound (A)>
The polymer compound (A) includes repeating units represented by the following formula (1) and the following formula (2).

（１）

(1)

（２）
式（１）中、Ｒ^１は、水素原子またはメチル基を表す。Ｒ^１は水素原子であることが好ましい。

(2)
In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a hydrogen atom.

  In formula (1), a represents an integer of 0 to 10. a is preferably 0.

In Formula (1), R ^a is an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or — A group represented by NHCOO- is represented. In the bond represented by “−”, the left hand may be the upper hand in Formula (1), and the right hand may be the upper hand in Formula (1). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. When there are a plurality of R ^{a s} , they may be the same or different. R ^a is preferably an alkylene group, a cycloalkylene group, or an arylene group, and more preferably an alkylene group or an arylene group.

Examples of the alkylene group represented by ^Ra 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.
Examples of the cycloalkylene group represented by ^Ra include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

Examples of the arylene group represented by ^Ra include a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, and a methyl group. Gate insulation obtained by using the composition of the present invention includes naphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and ethylanthrylene group. Since the dielectric loss tangent of the layer or the overcoat layer is excellent, a phenylene group is preferable.

  In formula (1), n represents an integer of 1 to 5. n is preferably 1.

  In formula (1), R represents a monovalent organic group that is eliminated from an oxygen atom by an acid. When there are a plurality of R, they may be the same or different. When an acid acts on the group represented by —OR, R is eliminated from the oxygen atom, and a group represented by the —OH group is generated.

  Examples of the monovalent organic group that is eliminated from the oxygen atom by the acid represented by R include, for example, a hydrofuranyl group, a hydropyranyl group, an alkyl group having an alkoxy group as a substituent at the 1st carbon atom, and a 1st carbon atom. And an alkyl group having a cycloalkoxy group as a substituent, a cycloalkyl group having an alkoxy group as a substituent at the 1st carbon atom, and a cycloalkyl group having a cycloalkoxy group as a substituent at the 1st carbon atom. These groups may have a substituent.

The hydrofuranyl group represented by R means a group excluding one hydrogen atom directly bonded to the carbon atom constituting the ring of dihydrofuran or tetrahydrofuran, and the substituent that the hydrofuranyl group may have is as follows. , An alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a hydroxyl group.
Examples of the hydrofuranyl group include a dihydrofuranyl group and a tetrahydrofuranyl group.

The hydropyranyl group represented by R means a group excluding one hydrogen atom directly bonded to the carbon atom constituting the dihydropyran or tetrahydropyran ring, and the substituent that the hydrofuranyl group may have Includes an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a hydroxyl group.
Examples of the hydropyranyl group include a dihydropyranyl group, a tetrahydropyranyl group, and a 4-methoxytetrahydropyranyl group.

  Examples of the substituent that the hydrofuranyl group and hydropyranyl group represented by R may have include a hydroxyl group, an alkoxy group, a cycloalkoxy group, an alkyl group, and a cycloalkyl group.

  Examples of the alkyl group represented by R having an alkoxy group as a substituent at the 1-position carbon atom include 1-methoxyethyl group, 1-ethoxyethyl group, 1-methoxypropyl group, and 1-ethoxypropyl group. Can be mentioned.

  An alkyl group having an alkoxy group as a substituent at the 1st carbon atom represented by R, an alkyl group having a cycloalkoxy group as a substituent at the 1st carbon atom, and an alkoxy group as a substituent at the 1st carbon atom Examples of the substituent that the cycloalkyl group may have and the cycloalkyl group having a cycloalkoxy group as a substituent at the 1st carbon atom may further include an ethyl group and a propyl group.

  R is preferably a 1-ethoxyethyl group.

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

  In formula (2), b represents an integer of 0 to 10. b is preferably 0.

In formula (2), R ^b represents an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or — A group represented by NHCOO- is represented. In the bond represented by “−”, the left hand may be the upper hand in Formula (2), and the right hand may be the upper hand in Formula (2). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. When there are a plurality of R ^{b s} , they may be the same or different. R ^b is preferably a group represented by —COO—, a group represented by —NHCO—, an alkylene group or an arylene group, a group represented by —COO—, and a group represented by —NHCO—. Or an alkylene group.

Examples of the alkylene group represented by ^Rb 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.

Examples of the cycloalkylene group represented by R ^b include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

Examples of the arylene group represented by R ^b include a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, and a methyl group. Examples include naphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and ethylanthrylene group.

R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. When there are a plurality of R ″, they may be the same or different. In one embodiment, R ″ is a hydrogen atom.
When R ″ is a monovalent organic group having 1 to 20 carbon atoms, the monovalent organic group having 1 to 20 carbon atoms does not have a fluorine 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, tertiary butyl group, and cyclopropyl. Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl 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, chlorophenyl group, bromophenyl group, etc. Cited .

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

  Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. When there are a plurality of Rf, they may be the same or different. Rf is preferably a fluorine atom. Specific examples of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by Rf include trifluoromethyl group, trifluoroethyl group, trifluorobutyl group, pentafluorobutyl group, and trifluoropentyl. Group, pentafluoropentyl group, heptafluoropentyl group, pentafluorophenyl group and trifluoromethylphenyl group.

  The polymer compound (A) is preferably a polymer compound that dissolves in an alcohol solvent at less than 5% by weight at 25 ° C. Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, trifluoroethanol, hexafluoro-2-propanol, Examples include pentafluoro-1-pentanol and octafluoro-1-pentanol.

  The polymer compound (A) includes, for example, a polymerizable monomer that is a raw material of a repeating unit having a group represented by the formula (1) and a polymerizable monomer that is a raw material of a repeating unit represented by the formula (2). And can be produced by copolymerization in the presence of a photopolymerization initiator or a thermal polymerization initiator.

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

  When light energy is used as the energy for initiating copolymerization, the wavelength of light applied to the polymerizable monomer is usually 360 nm or more, and preferably 360 nm or more and 450 nm or less.

  Any thermal polymerization initiator may be used as long as it is a radical polymerization initiator. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2′- Azobis (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylpropane) Azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride; ketone peroxide compounds such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide; isobutyl peroxide , Benzoyl peroxide, 2,4-dichlorobenzoyl peroxy Diacyl peroxide compounds such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, ortho-methylbenzoyl peroxide, lauroyl peroxide, para-chlorobenzoyl peroxide and the like; Hydroperoxide compounds such as oxide and tert-butyl hydroperoxide; Dialkyl peroxide compounds such as dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, and tris (tert-butylperoxy) triazine Peroxyketal compounds such as 1,1-di-tert-butylperoxycyclohexane and 2,2-di (tert-butylperoxy) butane; tert-butylperoxypivalate, te t-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3 , 5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, alkyl perester compounds such as di-tert-butylperoxytrimethyladipate; diisopropyl peroxydicarbonate, di-sec- Examples thereof include peroxycarbonate compounds such as butyl peroxydicarbonate and tert-butylperoxyisopropyl carbonate.

  As a monomer used as a raw material of the repeating unit represented by the formula (1), for example, 4- (1-ethoxyethoxy) styrene, 4- (2-pyranyloxy) styrene, 4- (2-ethyl-2-adamantyloxy) Styrene is mentioned.

  Examples of the monomer that is a raw material of the repeating unit represented by the formula (2) include 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2,3,4,5,6-pentafluorostyrene, 2 -Trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, vinyl-4-trifluoromethylphenyl ether, vinyl-2-trifluoromethylbenzoate, vinyl-3-trifluoromethylbenzoate, vinyl- 4-trifluoromethylbenzoate is mentioned.

  The polymer compound (A) includes a polymerizable monomer that is a raw material of a repeating unit having a group represented by the formula (1), and a polymerizable monomer that is a raw material of a repeating unit having a group represented by the formula (2) Alternatively, it may be produced by copolymerizing a polymerizable monomer which is a raw material for other repeating units.

  Examples of the polymerizable monomer used as a raw material for other repeating units include acrylic acid esters and derivatives thereof, methacrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl esters of organic carboxylic acids and derivatives thereof, and organic carboxylic acids. Allyl esters 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, N-vinylamide derivatives of organic carboxylic acids, terminal unsaturated hydrocarbons and derivatives thereof , Organic germanium derivatives containing an unsaturated hydrocarbon group, vinyl-1,3-dioxolan-2-one, and derivatives thereof.

  The kind of the polymerizable monomer that is the raw material for the other repeating unit is appropriately selected according to the characteristics required for the gate insulating layer or the overcoat layer. Since the durability to the solvent is excellent and the hysteresis of the organic thin film transistor is reduced, a polymerizable monomer that forms a hard film with high molecular density such as styrene and its derivatives is selected. Moreover, since the adhesiveness with a gate electrode and an adjacent layer is excellent, the polymerizable monomer which provides plasticity like a methacrylic ester and its derivative (s), an acrylic ester and its derivative (s) is selected.

  The acrylic ester and its derivative may be a monofunctional acrylate or a polyfunctional acrylate. Examples of acrylic acid esters and derivatives thereof include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-sec-butyl, and acrylic acid. Hexyl, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic Acid-3-hydroxypropyl, 2-hydroxybutyl acrylate, 2-hydroxyphenylethyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2 , 3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl- 2-hydroxypropyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (par Fluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3 -(Perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluorohept Tyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, N, N-dimethylacrylamide, N, N -Diethylacrylamide, N-acryloylmorpholine.

  The methacrylic acid ester and its derivative may be monofunctional methacrylate or polyfunctional methacrylate. Examples of methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Acid-sec-butyl, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, meta 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, methacrylate -Glycidyl phosphate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane tri Methacrylate, pentaerythritol pentamethacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 3- Perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxy Lopyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) Ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2- Hydroxypropyl methacrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) − 2-Hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexa Decafluorononyl methacrylate, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N -Acryloylmorpholine.

  Examples of styrene and derivatives thereof 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-bromostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hy Loxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-iso Propenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p- Examples include isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, and 4-aminostyrene.

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

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

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

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

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

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

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

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

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

  Examples of the polymerizable monomer used as a raw material for other repeating units include acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, 4-methoxystyrene, acrylonitrile, methacrylonitrile, allyltrimethylgermanium, or 4-vinyl-1,3-dioxolane. 2-one is preferred.

The repeating unit having a group represented by the formula (1) contained in the polymer compound (A) is preferably 10 mol% or more and 80 mol% or less with respect to all repeating units contained in the polymer compound (A). More preferably, it is 20 mol% or more and 60 mol% or less.
The repeating unit having a group represented by the formula (2) contained in the polymer compound (A) is preferably 5 mol% or more and 80 mol% or less with respect to all repeating units contained in the polymer compound (A). More preferably, it is 10 mol% or more and 80 mol% or less.

    The polystyrene equivalent weight average molecular weight of the polymer compound (A) is preferably 3,000 to 1,000,000, and more preferably 5,000 to 500,000.

Examples of the polymer compound (A) include:
Poly [4- (1-ethoxyethoxy) styrene-co-2,3,4,5,6-pentafluorostyrene], poly [4- (1-ethoxyethoxy) styrene-co-2,3,4,5,6 -Pentafluorostyrene-co-styrene], poly [4- (1-ethoxyethoxy) styrene-co-2,3,4,5,6-pentafluorostyrene-co-methyl-methacrylate],
Poly [4- (2-pyranyloxy) styrene-co-2,3,4,5,6-pentafluorostyrene], poly [4- (2-pyranyloxy) styrene-co-2,3,4,5,6 -Pentafluorostyrene-co-styrene], poly [4- (2-pyranyloxy) styrene-co-2,3,4,5,6-pentafluorostyrene-co-methyl-methacrylate],
Poly [4- (2-ethyl-2-adamantyloxy) styrene-co-2,3,4,5,6-pentafluorostyrene], poly [4- (2-ethyl-2-adamantyloxy) styrene-co -2,3,4,5,6-pentafluorostyrene-co-styrene], poly [4- (2-ethyl-2-adamantyloxy) styrene-co-2,3,4,5,6-pentafluoro Styrene-co-methyl-methacrylate],
Is mentioned.

  Only 1 type may be sufficient as the high molecular compound (A) contained in the composition of this invention, and 2 or more types may be contained.

<Compound (B)>
The compound (B) is a compound that decomposes by irradiation with electromagnetic waves or electron beams, or is heated to generate an acid, and is sometimes called a so-called acid generator.

  Examples of the electromagnetic wave include infrared rays, visible rays, and ultraviolet rays, and preferably ultraviolet rays. The wavelength of the electromagnetic wave is preferably 450 nm or less, more preferably 200 nm or more and 410 nm or less.

  When the compound (B) is a compound that decomposes by heating to generate an acid, the temperature at which the acid is generated is usually 200 ° C. or lower, preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher. It is 200 degrees C or less.

  Examples of the compound (B) include sulfonic acid ester compounds, triazine compounds, iodonium salts, sulfonium salts, and blocking acid compounds.

  As the sulfonic acid ester compound, a fluorinated alkyl sulfonic acid ester compound or a toluene sulfonic acid ester compound is preferable.

  Examples of the fluorinated alkyl sulfonic acid ester compound include N-hydroxynaphthalimide triflate, N-hydroxynaphthalimide perfluorobutyl triflate, N-hydroxyphthalimide triflate, and N-hydroxyphthalimide perfluorobutyl triflate. .

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

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

  Examples of the iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and tolylcumyl iodonium tetrakis (pentafluorophenyl) borate.

  Examples of the sulfonium salt include triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4,4′- Bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyl-di (4-methylphenyl) sulfonium hexafluoro Examples include phosphate.

  The block acid compound is a compound obtained by protecting an organic carboxylic acid, organic sulfonic acid, or organic phosphoric acid with an amine compound or an ether compound, such as an amine salt of p-toluenesulfonic acid or a quaternary ammonium salt of p-toluenesulfonic acid , An amine salt of trifluoromethanesulfonic acid, and a quaternary ammonium salt of trifluoromethanesulfonic acid.

  The compound (B) may be a sulfonium salt described in JP-A-9-118663 and an onium fluorinated alkyl fluorophosphate described in JP-A-2007-262401.

  Further, the compound (B) may be a compound that decomposes by irradiation with electromagnetic waves or electron beams and generates an acid by being decomposed by heating, and a temperature at which the acid is generated is 200 ° C. or higher. . In that case, it is preferable to use together with the compound (B) whose temperature which decomposes | disassembles by heating and generates an acid is 200 degrees C or less.

  Only 1 type may be sufficient as the compound (B) contained in the composition of this invention, and 2 or more types may be contained.

<Compound (C)>
Compound (C) is a compound that can react with a hydroxyl group in two or more polymer compounds (A) in the presence of an acid to form a crosslinked structure between the molecules of polymer compound (A).

  Examples of the compound (C) include melamine compounds and urea compounds.

  Examples of the melamine compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexabutoxymethyl melamine, poly (melamine-co-formaldehyde) methylated product, and poly (melamine-co-formaldehyde) methylated product.

  Examples of the urea compound include tetramethoxymethyl glycol urea and tetraethoxymethyl glycol urea.

  Only 1 type may be sufficient as the compound (C) contained in the composition of this invention, and 2 or more types may be contained.

（３）
式（３）中、Ｒ^１２は、水素原子又はメチル基を表す。Ｒ^１２は、メチル基であることが好ましい。式（３）中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１は、それぞれ独立に、水素原子又は炭素原子数１〜２０の１価の有機基を表す。該炭素原子数１〜２０の１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。Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１は、水素原子であることが好ましい。該炭素原子数１〜２０の１価の有機基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、ターシャリーブチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロペンチニル基、シクロヘキシニル基、フェニル基、ナフチル基、アンスリル基、トリル基、キシリル基、ジメチルフェニル基、トリメチルフェニル基、エチルフェニル基、ジエチルフェニル基、トリエチルフェニル基、プロピルフェニル基、ブチルフェニル基、メチルナフチル基、ジメチルナフチル基、トリメチルナフチル基、ビニルナフチル基、エテニルナフチル基、メチルアンスリル基、エチルアンスリル基、クロロフェニル基、ブロモフェニル基、トリフルオロメチル基、トリフルオロエチル基、ペンタフルオロプロピル基などが挙げられる。 <Compound (D)>
The composition of the present invention may further contain a compound (D) represented by the following formula (3).

(3)
In formula (3), R ¹² represents a hydrogen atom or a methyl group. R ¹² is preferably a methyl group. In formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. Represents an organic group. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are preferably hydrogen atoms. Specific examples of the monovalent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, and cyclopropyl. Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl 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, chlorophenyl group, bromophenyl group, triphenyl Fluoro Butyl group, trifluoroethyl group, and pentafluorophenyl propyl group.

  Examples of the compound (D) used in the present invention include 4-methacryloyloxybenzophenone, 2′-methyl-4-methacryloyloxybenzophenone, 3′-methyl-4-methacryloyloxybenzophenone, 4′-methyl-4-methacryloyl. And oxybenzophenone.

  From the viewpoint of increasing the withstand voltage of the insulating layer formed by the composition of the present invention, the compound (D) is preferably contained. When the compound (D) is further contained in the composition of the present invention, the compound (D) may be only one kind or two or more kinds.

  The part by weight of the compound (B) contained in the composition of the present invention is preferably 0.1 to 10 parts by weight, and 0.5 parts by weight with respect to 100 parts by weight of the polymer compound (A). To 5 parts by weight.

  The compound (C) contained in the composition of the present invention is preferably 0.1 to 100 parts by weight, preferably 1 to 80 parts by weight with respect to 100 parts by weight of the polymer compound (A). More preferably.

  In addition, the compound (C) contained in the composition of the present invention is 0.5 equivalent with respect to all hydroxyl groups generated by elimination of R by allowing the compound (B) to act on the polymer compound (A). To 3 equivalents, more preferably 0.7 equivalents to 2 equivalents.

  When the composition (D) is further contained in the composition of the present invention, the weight of the compound (D) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymer compound (A). Is preferred, and more preferably 1 to 30 parts by weight.

<Composition containing solvent>
The composition of the present invention may further contain a solvent, an additive and the like.
Examples of the solvent include ether solvents such as tetrahydrofuran and diethyl ether; aliphatic hydrocarbon solvents such as hexane; alicyclic hydrocarbon solvents such as cyclohexane; unsaturated hydrocarbon solvents such as pentene; aromatic hydrocarbons such as xylene. Solvents; ketone solvents such as acetone; acetate solvents such as butyl acetate; halogen solvents such as chloroform, and a mixture of these solvents.
Examples of the additive include a sensitizer, a leveling agent, and a viscosity modifier.
When the composition of this invention contains a solvent and an additive, solid content concentration is 5-40 wt% normally.

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

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

  A bottom gate top contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, an organic semiconductor layer formed on the gate insulating layer, and a source electrode formed on the organic semiconductor layer. And a drain electrode, and finally an overcoat layer. The composition of the present invention can be suitably used for forming a gate insulating layer. Moreover, the composition of this invention can be used suitably also for forming an overcoat layer.

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

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

<Method for producing membrane>
Formation of the gate insulating layer and / or overcoat layer of the organic thin film transistor is, for example,
A composition of the present invention (hereinafter also referred to as an insulating layer coating solution) containing the polymer compound (A), the compound (B), the compound (C) and a solvent is prepared, and the insulating layer coating solution is applied on the substrate. A step of forming a film by applying to the substrate and drying as necessary,
The compound (B) can be decomposed by heating or the like, and further heated to crosslink the molecules of the polymer compound (A) contained in the film with the compound (C). . Examples of means for decomposing the compound (B) other than heating include irradiation with electromagnetic waves or electron beams.

  By irradiating the coating film with an electromagnetic wave or an electron beam, the compound (B) decomposes to generate an acid, and R in the polymer compound (A) (a monovalent organic group that is desorbed from an oxygen atom by the acid) Is desorbed from the oxygen atom to form a hydroxyl group. The elimination reaction may be promoted by heating. Alternatively, by heating the coating film to a temperature equal to or higher than the thermal decomposition temperature of the compound (B), the compound (B) is thermally decomposed to generate an acid, and a hydroxyl group is generated as described above.

  Thereafter, by heating the coating film, the hydroxyl group in the produced polymer compound (A) reacts with the compound (C) in the presence of an acid generated by the decomposition of the compound (B), whereby two or more polymers are reacted. A structure in which the molecules of the compound (A) are cross-linked through the compound (C) is formed.

  Compound (D) can be further added to the composition of the present invention. By adding the compound (D), decomposition of the compound (B) by light is promoted, and since a new hydrophobic polymer structure is formed in the film, the leakage current is reduced and the withstand voltage is reduced. More improved.

  Here, the “base material” refers to a constituent member of an organic thin film transistor on which an insulating layer is to be formed. At least one of a gate electrode, a source electrode, a drain electrode, and an organic semiconductor layer is formed on the uppermost layer of the substrate.

  The insulating layer coating liquid can be applied onto the substrate by a known coating method such as a spin coating method, a die coater method, a reversal printing method, an ink jet printing method, or the like, and is dried as necessary. The solvent contained in the applied resin composition can be removed by drying.

  The wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 200 nm or more and 410 nm or less. As electromagnetic waves, ultraviolet rays are preferable.

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

  Heating can be performed using a hot plate and an oven.

  When the coating film is heated, it is usually heated for 5 minutes to 120 minutes at a temperature equal to or higher than the thermal decomposition temperature of the compound (B) that generates acid by thermal decomposition, preferably 10 minutes to 60 minutes. It is preferable to heat. Since the formed insulating layer has excellent crosslinkability and insulating properties, the heating temperature of the patterned film is preferably 80 ° C. or higher and 250 ° C. or lower, more preferably 100 ° C. or higher and 230 ° C. or lower.

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

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

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

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

As the organic semiconductor compound for forming the organic semiconductor layer 4, a π-conjugated polymer is used. For example, a polypyrrole polymer, a polythiophene polymer, a polyaniline polymer, a polyallylamine polymer, a fluorene polymer, a polycarbazole polymer, poly Indole polymers and poly (P-phenylene vinylene) polymers can be used.
Further, as the organic semiconductor compound for forming the organic semiconductor layer 4, a low molecular compound having solubility in a solvent is also used. For example, a polycyclic aromatic derivative such as pentacene, a phthalocyanine derivative, a perylene derivative, tetrathiaful. Valene derivatives, tetracyanoquinodimethane derivatives, fullerene compounds, and carbon nanotube compounds can be used. Specifically, for example, 2,1,3-benzothiadiazole-4,7-di (ethylene boronate) and 2,6-dibromo- (4,4-bis-hexadecanyl-4H-cyclopenta [2,1 -B; condensed compound with 3,4-b ']-dithiophene, 9,9-di-n-octylfluorene-2,7-di (ethylene boronate) and 5,5'-dibromo-2,2 Examples thereof include condensation compounds with '-bithiophene.

  The organic semiconductor layer is formed, for example, by dissolving an organic semiconductor compound in a solvent to prepare an organic semiconductor coating solution, applying the organic semiconductor coating solution on the gate insulating layer, and drying as necessary.

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

  The organic thin film transistor of the present invention may have an overcoat layer for the purpose of protecting the organic semiconductor layer and enhancing the smoothness of the surface. The overcoat layer may be a layer formed from the composition of the present invention.

  The insulating layer formed from the composition of the present invention can have a flat film or the like laminated thereon, and a laminated structure can be easily formed. For example, an organic electroluminescence element can be suitably mounted on the insulating layer.

  The organic thin film transistor of the present invention can be suitably used for an electronic device. Examples of the electronic device include an RFID tag, electronic paper, an organic electroluminescence display, and a sensor.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example.

Synthesis example 1
(Synthesis of polymer compound 1)
In a 125 ml pressure vessel (Ace), 18.46 g of 4- (1-ethoxyethoxy) styrene (Tosoh Organic Chemical Co., Ltd.), 5.00 g of styrene (Pure Chemical Co., Ltd.), 2, 3, 18.66 g of 4,5,6-pentafluorostyrene (manufactured by Aldrich), 0.21 g of 2,2′-azobis (2-methylpropionitrile), 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 63.50 g, in order to remove dissolved oxygen, it was bubbled with argon gas and sealed. The pressure vessel was immersed in an oil bath at 60 ° C. and reacted for 17 hours to obtain a viscous 2-heptanone solution in which the polymer compound 1 was dissolved. The polymer compound 1 is a polymer compound containing the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

高分子化合物１

Polymer compound 1

Synthesis example 2
Styrene (made by Wako Pure Chemical Industries) 2.06 g, 2,3,4,5,6-pentafluorostyrene (made by Aldrich) 2.43 g, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl -Methacrylate (made by Showa Denko, trade name “Karenz MOI-BM”) 1.00 g, 2,2′-azobis (2-methylpropionitrile) 0.06 g, 2-heptanone (made by Wako Pure Chemical Industries) 14.06 g Is put in a 50 ml pressure vessel (made by ACE), bubbled with nitrogen, sealed, and polymerized in an oil bath at 60 ° C. for 48 hours to form a viscous 2-heptanone solution in which the polymer compound 2 is dissolved. Got. The chemical structure of the polymer compound 2 is as follows.

高分子化合物２

合成例３
４−アミノスチレン（アルドリッチ製）３．５０ｇ、２，３，４，５，６−ペンタフルオロスチレン（アルドリッチ製）１３．３２ｇ、２，２’−アゾビス（２−メチルプロピオニトリル）０．０８ｇ、２−ヘプタノン（和光純薬製）２５．３６ｇを、１２５ｍｌ耐圧容器（エース製）に入れ、窒素をバブリングした後、密栓し、６０℃のオイルバス中で４８時間重合させて、高分子化合物３が溶解している粘稠な２−ヘプタノン溶液を得た。
高分子化合物３の化学構造は次の通りである。

Polymer compound 2

Synthesis example 3
4-aminostyrene (manufactured by Aldrich) 3.50 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 13.32 g, 2,2′-azobis (2-methylpropionitrile) 0.08 g 25-36 g of 2-heptanone (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 125 ml pressure vessel (manufactured by Ace), bubbled with nitrogen, sealed, and polymerized in an oil bath at 60 ° C. for 48 hours to obtain a polymer compound. A viscous 2-heptanone solution in which 3 was dissolved was obtained.
The chemical structure of the polymer compound 3 is as follows.

高分子化合物３

Polymer compound 3

Synthesis example 4
A 1L 4-neck round bottom flask equipped with an induction-stirred stirring blade, nitrogen-substituted inside, 500 ml equilibrium dropping funnel, Dimroth, 3-way cock, 53.79 g of methacryloyl chloride (manufactured by Tokyo Chemical Industry) and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) ) 300ml was added. While stirring with a stirring blade, a mixed solution of 85 g of 4′-hydroxybenzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), 64.97 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of tetrahydrofuran was slowly dropped over 2 hours at room temperature. . After completion of the dropwise addition, the reaction was further continued at room temperature for 12 hours. After completion of the reaction, the produced triethylamine hydrochloride was filtered off, and the filtrate was concentrated on a rotary evaporator. 200 ml of diethyl ether was added to the resulting viscous product, the insoluble material was filtered off, and the diethyl ether solution was transferred to a separatory funnel. The diethyl ether solution was washed twice with dilute hydrochloric acid and twice with an aqueous potassium carbonate solution, and then washed with ion-exchanged water until the aqueous layer became neutral, and the diethyl ether layer was separated. The diethyl ether layer was dried over anhydrous magnesium sulfate. After the salt was filtered off, the diethyl ether solution was concentrated to dryness with a rotary evaporator to obtain Compound 4 as a milky white wax. 93.65g yield

化合物４

Compound 4

Example 1
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 10.00 g of the 2-heptanone solution of the polymer compound 1 obtained in Synthesis Example 1 and a compound represented by the following formula (“MBZ-101” manufactured by Midori Chemical) as a photoacid generator 0.06 g, 0.59 g of hexamethoxymethyl melamine (“MW-390” manufactured by Sanwa Chemical Co., Ltd.) and 20.37 g of 2-heptanone were added and dissolved while stirring to prepare coating solution 1.

ＭＢＺ−１０１

MBZ-101

Example 1-1
<Formation of insulating layer>
The obtained coating solution 1 was filtered through a membrane filter having a pore size of 0.45 μm, and then spin-coated on a glass substrate with a chromium electrode. Then, the coating layer was formed by making it dry on a hotplate at 90 degreeC for 1 minute. Thereafter, the coating layer was irradiated with UV light (wavelength 365 nm) of 3200 mJ / cm ² using an aligner (manufactured by CANON Co., Ltd., PLA-521). Thereafter, the coating layer was cured by post-baking on a hot plate at 90 ° C. for 1 minute to obtain a gate insulating layer. Table 1 shows the curing temperature and curing time when forming the insulating layer.

  On the obtained gate insulating layer, an MIM (Metal Insulator Metal) element was manufactured by forming an aluminum electrode by vapor deposition using a metal mask.

Example 1-2
<Evaluation of electrical characteristics of MIM element>
The dielectric loss tangent and dielectric strength of the manufactured MIM element were measured using a vacuum probe (manufactured by Nagase Electronic Equipments Service Co., LTD, BCT22MDC-5-HT-SCU). Here, the withstand voltage was evaluated by an electrolytic strength at which a leak current was 1 × 10 ⁻⁶ A / cm ² when an electric field was applied between the electrodes. Table 2 shows the results.

Example 2
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 10 ml sample bottle, 10.00 g of the 2-heptanone solution of polymer compound 1 obtained in Synthesis Example 1 and a compound represented by the above formula as a photoacid generator (“MBZ-101” manufactured by Midori Chemical) 0.06 g, 0.59 g of hexamethoxymethylmelamine (“MW-390” manufactured by Sanwa Chemical Co., Ltd.), 0.40 g of compound 4 obtained in Synthesis Example 4, and 22.60 g of 2-heptanone were added and dissolved while stirring. Thus, a coating solution 2 was prepared.

Example 2-1
<Formation of insulating layer>
The obtained coating solution 2 was filtered through a membrane filter having a pore diameter of 0.45 μm, and then spin-coated on a glass substrate with a chromium electrode. Then, the coating layer was formed by making it dry on a hotplate at 90 degreeC for 1 minute. Thereafter, the coating layer was irradiated with UV light (wavelength 365 nm) of 3200 mJ / cm ² using an aligner (manufactured by CANON Co., Ltd., PLA-521). Thereafter, the coating layer was cured by post-baking on a hot plate at 90 ° C. for 1 minute to obtain a gate insulating layer. Table 1 shows the curing temperature and curing time when forming the insulating layer.

  On the obtained gate insulating layer, an MIM (Metal Insulator Metal) element was manufactured by forming an aluminum electrode by vapor deposition using a metal mask.

Example 2-2
<Evaluation of electrical characteristics of MIM element>
The dielectric loss tangent and dielectric strength of the manufactured MIM element were measured using a vacuum probe (manufactured by Nagase Electronic Equipments Service Co., LTD, BCT22MDC-5-HT-SCU). Here, the withstand voltage was evaluated by an electrolytic strength at which a leak current was 1 × 10 ⁻⁶ A / cm ² when an electric field was applied between the electrodes. Table 2 shows the results.

Comparative Example 1
(Manufacture of organic thin film transistor insulating layer materials and MIM elements)
In a 200 ml sample bottle, 21.31 g of the 2-heptanone solution of the polymer compound 2 obtained in Synthesis Example 2, 12.64 g of the 2-heptanone solution of the polymer compound 3 obtained in Synthesis Example 3, and 2-heptanone A coating solution 3 was prepared by adding 73.08 g and dissolving with stirring.

Comparative Example 1-1
<Formation of insulating layer>
The obtained coating solution 3 was filtered through a membrane filter having a pore diameter of 0.45 μm, and then spin-coated on a glass substrate with a chromium electrode. Then, the coating layer was formed by making it dry on a hotplate at 90 degreeC for 1 minute. Then, the coating layer was hardened by post-baking at 200 ° C. for 30 minutes on a hot plate in nitrogen to obtain a gate insulating layer. Table 1 shows the curing temperature and curing time when forming the insulating layer.

  By using the composition of the present invention, the gate insulating layer or the overcoat layer can be formed at a low curing temperature. Further, by using the composition of the present invention, the gate insulating layer or the overcoat layer can be formed in a short curing time. In addition, the gate insulating layer or overcoat layer formed from the composition of the present invention exhibits good dielectric loss tangent and dielectric strength.

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

Claims (10)

A polymer compound (A) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and generating an acid by decomposition by irradiation with electromagnetic waves or electron beams, or heating. And a compound (C) capable of reacting with two or more hydroxyl groups in the presence of an acid to form a crosslinked structure between molecules of the polymer compound (A).

(1)
[Wherein, R ¹ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 10, and n represents an integer of 1 to 5. R ^a is represented by an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or —NHCOO—. Represents a group. In the bond represented by “−”, the left hand may be the upper hand in Formula (1), and the right hand may be the upper hand in Formula (1). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. R represents a monovalent organic group that is eliminated by an acid. When there are a plurality of R, they may be the same or different. ]

(2)
[Wherein R ² represents a hydrogen atom or a methyl group. b represents an integer of 0 to 10, and m represents an integer of 1 to 5. R ^b is an alkylene group, a cycloalkylene group, an arylene group, a group represented by —CO—, a group represented by —COO—, a group represented by —NHCO—, or a group represented by —NHCOO—. Represents a group. In the bond represented by “−”, the left hand may be the upper hand in Formula (2), and the right hand may be the upper hand in Formula (2). There may be. Among these, the hydrogen atom which an alkylene group, a cycloalkylene group, and an arylene group have may be substituted by the fluorine atom. When there are a plurality of R ^{b s} , they may be the same or different. R ″ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms does not have a fluorine atom. When there are a plurality of R ″, they may be the same or different. Rf represents a C1-C20 monovalent organic group which has a fluorine atom or a fluorine atom. When there are a plurality of Rf, they may be the same or different. ] The composition according to claim 1, wherein the compound (B) is a sulfonic acid ester compound, a triazine compound, a sulfonium salt, an iodonium salt, or a blocking acid compound. The composition according to claim 1 or 2 , wherein the compound (C) is a melamine compound or a urea compound. Furthermore, the composition as described in any one of Claims 1-3 containing the compound (D) represented by following formula (3).

(3)
[Wherein, R ¹² represents a hydrogen atom or a methyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ] Furthermore, the composition as described in any one of Claims 1-4 containing a solvent. Applying the composition according to claim 5 on a substrate to form a film;
And a step of crosslinking the molecules of the polymer compound (A) contained in the film via the compound (C) . A film manufactured by the manufacturing method according to claim 6 . The organic thin-film transistor which has the film | membrane of Claim 7 in an insulating layer. The organic thin-film transistor according to claim 8 , wherein the insulating layer is a gate insulating layer and / or an overcoat layer. Electronic device having an organic thin film transistor according to claim 8 or 9.

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